Crystalline Modification of Fipronil

ABSTRACT

The present invention relates to a crystalline modification of fipronil, to a process for the preparation of the same, to pesticidal and parasiticidal mixtures and compositions comprising said crystalline modification and to their use for combating pests and parasites.

The present invention relates to a novel crystalline modification of fipronil, to a process for the preparation of the same, to pesticidal and parasiticidal mixtures and compositions comprising said crystalline modification and to their use for combating pests and parasites.

Fipronil (formula I) is an active compound for controlling certain insect and acarid pests, and parasites.

Various processes for the preparation of fipronil have been described, generally and in detail. Documents which give detailed preparation procedures are e.g. EP 295 117; EP 460 940; EP 484 165; EP 668 269; EP 967 206; EP 1 331 222; EP 1 374 061; U.S. Pat. No. 5,631,381; CN 1374298; or J. of Heibei University of Science and Technology, Vol. 25 (2), Sum 69 (2004), Dok. Serial No. 1008-1542 (2004) 02-0018-03.

Characterization of the fipronil material obtained by the processes described in the prior art is usually done by ¹H-NMR analysis and/or measurement of the melting point. The described melting points are in the range of from 187° C. to 203° C., mostly in the range of from 195° C. to 203° C. In the Pesticidal Manual, 13^(th) Edition (2003), British Crop Protection Council, p. 433, fipronil is described as a white solid with a melting point of 200 to 201° C., with technical fipronil having a melting point of 195.5° C. to 203° C. Observations of different crystalline forms of fipronil have not been described, let alone any characterization of a certain crystalline modification or a preparation procedure for obtaining a certain crystalline modification.

For the large-scale preparation and formulation of a market compound such as fipronil, it is of crucial importance to know whether different crystalline modifications (also frequently referred to as polymoprhs) of a compound exist, how they can be obtained, and what their characteristic properties are. Crystalline modifications of one compound may have very different properties, for example with regard to solubility, rate of dissolution, suspension stability, stability during grinding, vapour pressure, optical and mechanical properties, hygroscopicity, crystal size, filtration properties, desiccation, density, melting point, degradation stability, stability against phase transformation into other crystalline modifications, colour, and even chemical reactivity.

For example, different crystalline modifications frequently manifest themselves in different forms of the crystals, such as needles or plates. This is of relevance for e.g. a filtration step in the preparation procedure. In such mixtures of different crystalline modifications plates typically will clog the pores of a filter leading to loss of time and product and tedious and expensive cleaning work. Also, a crystalline modification being present as plates and a crystalline modification being present as needles can have significantly different bulk densities which has implications for storage and packaging. Another relevant aspect, especially in the production of pesticides, is whether the crystalline modification is present as a fine powder which can produce hazardous dusts, or as dust-free larger crystals. Different modifications of fipronil have different bulk densities and mixtures of unpredictable ratios thereof create the afore-mentioned problems in storage and packaging.

Against this background, it has been an object of the present invention to find and characterize a novel crystalline modification of fipronil.

A further object has been to find preparation procedures for the novel crystalline modification which reproducibly give the crystalline modification I.

Another object of the invention has been to find preparation procedures which give the novel crystalline modification I in high yield.

Yet another object of the invention has been to find preparation procedures which give the novel crystalline modification essentially excluding other crystalline modification forms (i.e. in over 80% by weight). This ensures reproducibility and stability in all aspects of the production, transportation, storage and use of the corresponding solid state form.

Accordingly, a novel crystalline modification of fipronil, a process for its preparation, pesticidal and parasiticidal mixtures and compositions comprising it and its use for combating pests and parasites has been found. The novel crystalline modification of fipronil is defined as “novel crystalline modification I” throughout this application.

Also, most suprisingly, 3 other crystalline modifications of fipronil have been found, which are subject to co-pending patent applications. Especially surprising was that the present crystalline modification I of fipronil has a very similar melting point as a second crystalline modification V, both melting points lying in the range of the melting points given in the prior art (i.e. 195 to 203° C.). Moreover, two further crystalline modifications II and IV of fipronil, as described in co-pending patent applications, undergo phase transformations during heating into the more stable forms I and V, and thus in a typical melting point measurement will give the melting points of these forms I and II. The solid forms of fipronil thus are part of a very complex crystallization scenario. It can be concluded that the melting points given in the literature in no way can indicate which crystalline modification or crystalline modification mixtures were analyzed.

In T 605/02, the Technical Board of Appeal of the European Patent Authority ruled that, in the absence of a respective described preparation procedure, even the XRD pattern of a certain crystalline modification does not constitute prior art for lack of enablement. Thus, melting points given in documents published prior to the filing of this application cannot be regarded as prior art for the present invention as they do not enable the artisan to prepare the novel crystalline modification of fipronil.

The novel crystalline modification I of fipronil is present in a monoclinic crystal system having the centrosymmetric space group C2/c (herein also referred to as “crystalline modification I”, or “modification I”, or “crystalline modification”).

This invention further relates to a crystalline modification I of fipronil which, shows in an X-ray powder diffractogram recorded using Cu—Kα radiation (1.54178 Å) at 25° C. shows 4, in particular at least 6, especially 7 and preferably all of the following reflections quoted below as reflections quoted below as interplanar spacings d or as 2θ values:

d=7.45±0.1 Å 2θ=11.8±0.2°  (1)

d=6.07±0.07 Å 2θ=14.5±0.2°  (2)

d=5.57±0.05 Å 2θ=15.8±0.2°  (3)

d=4.84±0.05 Å 2θ=18.2±0.2°  (4)

d=3.76±0.05 Å 2θ=23.6±0.2°  (5)

d=3.67±0.05 Å 2θ=24.1±0.2°  (6)

d=3.23±0.05 Å 2θ=27.4±0.2°  (7)

d=3.01±0.05 Å 2θ=29.5±0.2°  (8)

d=2.77±0.05 Å 2θ=32.2±0.2°  (9)

In a particularly preferred embodiment, the crystalline modification I exhibits a powder X-ray diffraction pattern substantially the same as the pattern shown in FIG. 1.

Studies of single crystals of the crystalline modification I have shown that the basic crystal structure is monoclinic and has the space group C2/c. The characteristic data of the crystal structure of the crystalline modification I, are shown in Table 1.

TABLE 1 Crystallographic data of the crystalline modification I Parameter Modification I Class Monoclinic Space group C2/c a 22.246(2) Å b 12.704(1) Å c 14.626(2) Å α 90.00° β 128.889(1)° γ 90.00° Volume 3217.3(4) Å³ Z 8 Temperature −173.2° C. Density (calculated) 1.81 g/cm³ R1, ωR2 0.052, 0.112 a, b, c = Length of the unit cell edges α, β, γ = Angles of the unit cell Z = Number of molecules in the unit cell

The crystalline modification I of fipronil has typically a melting point in the range from 180 to 200° C., in particular in the range from 190 to 200° C. and especially in the range from 196 to 198° C., in essentially pure form of 197° C.

The differential scanning calorimetry (DSC) thermogram of the crystalline modification I of fipronil contains an endotherm with an onset temperature of from 194° C. to 197° C. and a peak maximum of 196° C. to 199° C. It is shown in FIG. 2.

In another embodiment, the present invention relates to the crystalline modification I having a fipronil content of at least 92% by weight, particularly at least 96% by weight and especially at least 98% by weight.

This invention also relates to solid (compositions of) fipronil comprising the crystalline modification I as defined hereinabove and a form of fipronil being different from said crystalline modification I (herein also referred to as “fipronil form”), e.g. amorphous fipronil or fipronil of a crystalline modification different from crystalline modification I. Preferably, the solid (compositions of) fipronil comprise the crystalline modification I in at least 85% by weight, preferably in at least 90% by weight, more preferably in at least 95% by weight, and most preferably in at least 98% by weight.

Modification I, which is obtainable by the processes according to the invention, crystallises in form of plates or platelets. Compared to other modifications of fipronil it raises less dust, and eases filtration and drying in the preparation procedure. Such novel crystalline modification I further provides high formulation stability of solid fipronil compositions.

The crystalline modification I can be prepared using a process which comprises the following steps:

-   step i) preparing a solution of a solid form of fipronil being     different from the crystalline modification I in a solvent S     comprising at least one alcohol A1, acetonitrile, dimethylsulfoxide     (DMSO), or at least one benzene derivative B1 or a mixture thereof,     which solvent S may be combined with another solvent AS; -   step ii) effecting crystallization of fipronil; and -   step iii) isolating the resulting precipitate.

Alcohols A1 according to the present invention are C₁-C₄-alkanols, i.e. methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-butanol, or tert-butanol.

Benzene derivatives B1 are inert under the process conditions, and consist preferably of benzene, which may be substituted by one or more groups selected from halogen, cyano, C₁-C₆-alkyl, C₁-C₆-alkoxy, halogenmethyl, and nitro, such as fluorobenzene, benzonitrile, anisole, p-xylene, o-xylene, m-xylene, CF₃-benzene, i-propylbenzene, n-propylbenzene, n-butylbenzene, t-butylbenzene, s-butylbenzene, i-butylbenzene, chlorobenzene, 2-chlorotoluene, 4-chlorotoluene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,4-diisopropylbenzene, mesitylene, nitrobenzene, 2-nitrotoluene, 3-nitrotoluene, 4-nitrotoluene, n-propylbenzene, and toluene, and is more preferably selected from mono-, di- or tri(C₁-C₆-alkyl)benzenes, which may be halogenated.

In one embodiment such another solvent AS may be a non-polar solvent N, which reduces the solubility of fipronil in the solvent S, such as hydrocarbons, preferably C₅-C₁₄-alkanes, e.g. pentane, hexane, heptane, octane, nonane, decan, undecan, or dodecan, or mixtures thereof.

In another embodiment such another solvent AS may be a polar solvent P. The addition of a solvent P may assist the crystallisation of modification I from the solution.

Polar solvent P is preferably selected from the group of methanol, ethanol, propan-1-ol, propan-2-ol (isopropanol), butan-1-ol (n-butanol), butan-2-ol, tert-butanol, 2-methylpropan-1-ol (iso-butanol), 2-methyl-propan-2-ol, pentan-3-ol, 2-methyl butan-1-ol, 3-methyl butan-1-ol, 1,2-ethanediol, 1,3-propandiol, 1,2-propandiol, cyclohexanol, acetonitrile, propionitrile, acetone, butanone (methyl ethyl ketone), pentan-2-one (methyl propyl ketone), pentan-3-one (diethylketone), 4-methyl-2-pentanone (isobutylmethyl-ketone), 3-methyl-butan-2-one (iso-propyl-methyl-ketone), 3,3-dimethyl-2-butanone (tert-butyl-methyl-ketone), cyclohexanone, methylacetate, ethylacetate, isopropylacetate, N-butylacetate, isobutylacetate, diethylcarbonate, 2-butoxyethylacetate, dioxane, tetrahydrofuran (THF), diethylether, 2-methyl-THF, methyl-tert-butylether, dimethylformamide, dimethylacetamide, dimethylsulfoxide (DMSO), nitromethane, and nitroethane.

Usually C₂-C₄-alcohols, ketones and acetates are preferred as polar solvents P in the inventive process.

In one embodiment the solvent P is present from the beginning of step i), it can form up to 50% by volume of the solvent used, preferably up to 20%, most preferred 5 to 15%.

In another embodiment the solvent P is added after step i) is completed.

A detailed description of these steps is as follows:

Step i)

Suitable fipronil forms different from the crystalline modification I used in step i) are, for example, selected from amorphous fipronil or crystalline fipronil such as triclinic fipronil of the space group P-1, and also mixtures of crystalline modifications of fipronil.

The fipronil form used as starting material in step i) preferably has a purity of at least 85% by weight, in particular at least 90% by weight and especially at least 95% by weight. “Purity” means the absence of chemical compounds other than fipronil.

The solvent S used in step i) comprises at least one alcohol A1. Solvent S may additionally contain water.

In another embodiment S may be acetonitrile or DMSO, which may additionally contain water or a polar solvent P. In a further embodiment S may be at least one benzene derivative B1, optionally in combination with a polar solvent P. The polar solvent P is usually applied in a ratio of at least 5 vol.-%, and up to 20 vol.-%, preferably up to 15 vol.-% of the over-all solvent volume.

Solvent S preferably is selected from:

-   (a) a pure alcohol A1, -   (b) a mixture of different alcohols A1, -   (c) a mixture of one or more alcohols A1 with water, -   (d) pure acetonitrile, -   (e) a mixture of acetonitrile with water and/or one or more     additional solvents AS, which preferably consist of polar solvents     P, -   (f) pure DMSO, -   (g) a mixture of DMSO with water and/or one or more additional     solvents AS, which preferably consist of polar solvents P, -   (h) pure benzene derivative B1, -   (i) a mixture of one or more benzene derivatives B1 with one or more     alcohols A1, and -   (j) a mixture of one or more benzene derivatives B1 with one or more     additional solvents AS, which preferably consist of polar solvents     P.

Particularly preferred alcohols A1 are methanol, ethanol, and isopropanol.

In a preferred embodiment, the solvent S used in step i) consists of methanol, ethanol, or isopropanol, preferably methanol.

In another embodiment, the solvent S used in step i) consists of a mixture of an alcohol A1 as defined hereinabove and water. The proportion of water will preferably not exceed about 25% by weight, based on the total amount of the solvent S.

Benzene derivatives B1 according to the present invention are mono-, di- or tri(C₁-C₆-alkyl)benzenes, which may be halogenated, preferably ethyl benzene, n-propyl benzene, isopropyl benzene, di isopropyl benzene, n-butyl benzene, t-butyl benzene, s-butyl benzene, iso-butyl benzene, CF₃-benzene, 2-chloro toluene, 3-chloro toluene and mesitylene.

Particularly preferred benzene derivatives B1 are ethyl-, di isopropyl-, n-butyl benzene, and CF₃-benzene.

In a preferred embodiment, the solvent S used in step i) consists of a mixture of a benzene derivative B1, preferably selected from ethyl-, di isopropyl-, n-butyl benzene, and CF₃-benzene, and at least one solvent selected from acetone, acetates, ketones, or alcohols A1, which alcohol is preferably selected from ethanol or isopropanol.

In another preferred embodiment, the solvent S used in step i) consists of a mixture of a benzene derivative B1, preferably selected from ethyl-, di isopropyl-, n-butyl benzene, and CF₃-benzene, and a polar solvent P as defined and preferred above.

In case the solvent S is acetonitrile, crystallisation step ii) is preferably conducted by evaporating the solvent at low temperatures, such as temperatures below 40° C., preferably 20-25° C., most preferred 0-20° C.

In case the solvent S is DMSO, crystallisation step ii) is preferably conducted at temperatures below 80° C., preferably below 50° C., such as at 20-25° C., preferably 0-20° C. Precipitation is preferably made by adding a polar solvent P or water, preferably water.

In step i), the fipronil form different from the crystalline modification I will usually be incorporated into the solvent S as a solid with mixing at a concentration and temperature where the solvent S is capable of completely dissolving the fipronil form.

In a preferred embodiment of the invention, the fipronil form is dissolved at an elevated temperature, preferably from 30 to 60° C. and particularly preferably in the range from 40 to 50° C. The amount of fipronil form dissolved in the solvent S depends, on the nature of the solvent S and on the dissolution temperature. The person skilled in the art will be able to determine suitable conditions by standard experiments.

In a case, where the solvent S consists of methanol, the temperature range for dissolving the fipronil form is from 20 to 60° C., in particular in the range of from 40 to 50° C.

In a case, where the solvent S consists of a benzene derivative B1, especially ethyl-, di isopropyl-, n-butyl benzene, and CF₃-benzene, the temperature range for dissolving the fipronil form is usually above 90° C., preferably from 100 to 140° C., in particular in the range of from 110 to 120° C.

Step ii)

In step ii) of the process of this invention, fipronil is then crystallized. Crystallization can be effected in a customary manner, for example by cooling the solution obtained in step i), by adding a solvent which reduces the solubility (in particular by adding water), or by concentrating the solution, or by a combination of the measures mentioned above.

In one embodiment of the above described process step, the added solvent, which reduces the solubility, consists of a polar solvent P.

In a preferred embodiment, step ii) is carried out in the presence of seed crystals of the crystalline modification I.

To achieve a conversion into the crystalline modification I which is as complete as possible, the crystallization is carried out over a period (duration of crystallization) of at least 1 h, in particular at least 3 h. Duration of crystallization is understood by the person skilled in the art as meaning the period of time between the beginning of the measure which initiates crystallization and the isolation of the fipronil by separating the crystalline material from the mother liquor.

In general, the crystallization is allowed to proceed to a point where at least 60%, preferably at least 70%, in particular at least 90% by weight, for example from 80 to 90% by weight, of the fipronil employed has crystallized out.

Cooling of the solution typically is effected at a cooling rate of 5 to 20 K per hour, preferably starting at an elevated temperature close to the boiling point of the solvent S, preferably not above 90° C., more preferred not above 80° C. For example, in case where the solvent S consists of ethanol, cooling is done starting at 60° C. and at a rate of 10 K per hour. Cooling rates are usually adjusted in the range of 5 to 20 K/h, preferably up to 10 K/h.

Concentration of the solution is effected by gradually removing the solvent S, such as by evaporation in vacuum, either at low temperature or at about 20-25° C. or at elevated temperature, and/or in the presence of a flow of an inert gas such as nitrogen or argon. The values of “low temperature” and “elevated temperature” depend, of course, on the nature of the solvent S and will be readily determined by the skilled artisan. For example, in case where the solvent S consists of methanol, evaporation is preferably done at 18 to 27° C. in air or at 40° C. to 50° C. in a nitrogen flow.

Preferably, crystalline modification I is obtained from solutions of fipronil at temperatures of 0° C. to 25° C.

It is particularly preferred that the crystallization of fipronil is effected by adding water to the solution of fipronil obtained in step i), for example from 20 to 130% by weight, in particular from 50 to 130% by weight and especially from 100 to 130% by weight of water, based on the weight of the solvent S used for dissolving the fipronil form. The addition of water is preferably carried out over a relatively long period of time, for example over a period of from 15 min to 4 h, in particular over a period of from 0.5 h to 2 h. Preferably, the resulting mixture is continuously stirred after addition of water. The person skilled in the art will be able to determine the amount of water necessary to effect crystallization.

In another preferred embodiment, the crystallization of fipronil is effected by the successive addition of a first amount of a solvent which reduces the solubility (preferably water), and then seed crystals of the crystalline modification I.

In general, the yield of crystallization may be further enhanced by cooling to temperatures lower than 20° C., preferably to a temperature of from 0 to 10° C.

In a preferred embodiment, the crystallization is effected by concentrating the solution. From certain solvents, such as toluene, fluoro benzene, xylene, MCB, or DCB, fipronil may be cristallised by cooling the hot solution to at least 75° C., and tempering the precipitate at up to 100° C., preferably up to 95° C., more preferred up to 90° C. Such tempering, until conversion to modification I is completed, usually takes about 12 to 48 hours. The time of tempering depends also of the applied pressure.

The crystallisation may be conducted under reduced pressure, such as less than 100 bar, preferred 5 to 40 mbar.

When cooling the solution the begin of crystallisation is effected in a temperature range of 60 to 100° C., preferred of 70 to 90° C., depending from saturation of the solution. A person skilled in the art is able to effect the crystallization temperature by the means of adjusting the combination of concentration, cooling rate and addition of seed crystals in the crystallization solution.

Step iii)

In step iii) of the process of this invention, the crystalline modification I is isolated using customary techniques for separating solid components from liquids, for example by filtration, centrifugation or decanting. In general, the isolated precipitate will be washed, for example with the solvent S used for the crystallization. The washing can be carried out in one or more steps. The washing is typically carried out at temperatures lower than 30° C. and in particular lower than 25° C., to keep the loss of the product of value as low as possible. The resulting crystalline fipronil or modification I can then be dried and subjected to further processing.

Isolating of modification I can also be achieved by evaporation from acetonitrile at 20 to 35° C.

Alternatively isolation of modification I can also be achieved by precipitation from acetonitrile or DMSO with water.

The preparation process consisting of steps i) to step iii) can be repeated in order to achieve higher purities of fipronil.

The crystalline modification I is especially suitable for efficiently combating the following pests:

millipedes (Diplopoda) such as Blaniulus or Narceus ssp; insects (Insecta) such as: ants, bees, wasps, sawflies (Hymenoptera), e.g. Atta capiguara, Atta cephalotes, Atta laevigata, Atta robusta, Atta sexdens, Atta texana, Crematogaster spp., Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata, Solenopsis invicta, Solenopsis richteri, Solenopsis xyloni, Pheidole megacephala, Pogonomyrmex species such as Pogonomyrmex barbatus and Pogonomyrmex californicus, Dasymutilla occidentalis, Bombus spp. Vespula squamosa, Paravespula vulgaris, Paravespula pennsylvanica, Paravespula germanica, Dolichovespula maculata, Vespa crabro, Polistes rubiginosa, Camponotus floridanus, and Linepithema humile, beetles (Coleoptera), such as Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus and other Agriotes species, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Aracanthus morei, Atomaria kneads, Blapstinus species, Blastophagus piniperda, Blitophaga undata, Bothynoderes punciventris, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus and other Conoderus species, Conorhynchus mendicus, Crioceris asparagi, Cylindrocopturus adspersus, Diabrotica (longicornis) barber, Diabrotica semi-punctata, Diabrotica speciosa, Diabrotica undecimpunctata, Diabrotica virgifera and other Diabrotica species, Eleodes species, Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus brasffiensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californicus and other Limonius species, Lissorhoptrus oryzophilus, Listronotus bonariensis, Melanotus communis and other Melanotus species, Meligethes aeneus, Melolontha hippocastani; Melolontha melolontha, Oulema oryzae, Ortiorrhynchus sulcatus, Oryzophagus oryzae, Otiorrhynchus ovatus, Oulema oryzae, Phaedon cochleariae, Phyllotreta chrysocephala, Phyllophaga cuyabana and other Phyllophaga species, Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, and other Phyllotreta species, Popillia japonica, Promecops carinicollis, Premnotrypes voraz, Psylliodes species, Sitona lineatus, Sitophilus granaria, Sternechus pinguis, Sternechus subsignatus, and Tanymechus palliatus and other Tanymechus species, Centipedes (Chilopoda), e.g. Scutigera coleoptrata, Cockroaches (Blattaria-Blattodea), e.g. Blattella germanica, Blattella asahinae, Periplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blatta orientalis, Crickets, grasshoppers, locusts (Orthoptera), e.g. Acheta domestics, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femurrubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Schistocerca americana, Schistocerca gregaria, Dociostaurus maroccanus, Tachycines asynamorus, Oedaleus senegalensis, Zonozerus variegatus, Hieroglyphus daganensis, Kraussaria angulifera, Calliptamus italicus, Chortoicetes terminifera, and Locustana pardalina, fleas (Siphonaptera), e.g. Ctenocephalides fells, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus, Flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, Agromyza oryzea, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Contarinia sorghicola, Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Delia antique, Delia coarctata, Delia platura, Delia radicum, Dermatobia hominis, Fannia canicularis, Gasterophilus intestinalis, Geomyza Tripunctata, Glossina morsitans, Glossine palpalis, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hypoderma lineata, Leptoconops torrens, Liriomyza sativae, Liriomyza trifolii, Lucilia caprin, Lucilia cuprina, Luculia sericata, Lycoria pectoralis, Mansonia spp., Mayetiola destructor, Musca domestica, Muscina stabulans, Oestrus ovis, Oestrus ovis, Opomyza florum, Oscinella frit, Pegomya hysocyami, Phlebotomus argentipes, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Progonya leyoscianii, Psila rosae, Psorophora columbiae, Psorophora discolor, Prosimulium mixtum, Rhagoletis cerasi, Rhagoletis pomonella, Sarcophaga haemorrhoidalis, Sarcophaga sp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, Tabanus similis, Tetanops myopaeformis, Tipula olerace, and Tipula paludosa, Heteropterans (Heteroptera), such as Acrosternum hilare, Blissus leucopterus, Cicadellidae such as Empoasca fabae, Chrysomelidae, Cyrtopeltis notatus, Delpahcidae, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nephotettix species, Nezara viridula, Pentatomidae, Piesma quadrata, Solubea insularis and Thyanta perditor, Aphids and other homopterans (Homoptera), e.g. Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphis glycines, Aphis gossypii, Aphis grossulariae, Aphis pomi, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum solani, Brachycaudus cardui, Brachycaudus helichrysi, Brachycaudus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, Dysaphis plantaginea, Dysaphis pyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus lactucae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Melanaphis pyrarius, Metopolophium dirhodum, Myzodes (Myzus) persicae, Myzus ascalonicus, Myzus cerasi, Myzus varians, Nasonovia ribis-nigri, Nilaparvata lugens, Pemphigus bursarius, Pemphigus populivenae, and other Pemphigus species, Perkinsiella saccharicida, Phorodon humuli; Psyllidae such as Psylla mali; Psylla piri and other Psylla species, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Rhopalosiphum padi, Rhopalosiphum insertum, Sappaphis mala, Sappaphis mali; Schizaphis graminum, Schizoneura lanuginosa, Sitobion avenae, Trialeurodes vaporariorum, Toxoptera aurantiiand, and Viteus vitifolii, Lepidopterans (Lepidoptera), for example Agrotis ypsilon, Agrotis segetum and other Agrotis species, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobia brumata, Chilo suppresalis and other Chilo species, Chodstoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cnaphlocrocis medinalis, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Euxoa species, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha molesta, Hellothis armigera, Heliothis virescens, Heliothis zea, Hellula undalis, Hibernia defokiaria, Hyphantria cunea, Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina fiscellaria, Laphygma exigua, Lerodea eufala, Leucoptera coffeella, Leucoptera scitella, Lithocolletis blancardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae, Momphidae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scabra, Plutella xylostella, Pseudoplusia includens, Rhyacionia frustrana, Scrobipalpula absoluta, Sesamia nonagrioides and other Sesamia species, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Tfichoplusia ni and Zeiraphera canadensis, lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus, orthopterans (Orthoptera), such as Acrididae, Acheta domestica, Forficula auricularia, Gryllotalpa gyllotalpa, Locusts migratoria, Melanoplus bivittatus, Melanoplus femurrubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Schistocerca americana, Schistocerca peregrina, Stauronotus maroccanus and Tachycines asynamorus, silverfish, firebrat (Thysanura), e.g. Lepisma saccharin and Thermobia domestica, termites (Isoptera), such as Calotermes flavicollis, Coptotermes ssp., Dalbulus maidis, Heterotermes aureus, Leucotermes flavipes, Macrotermes gilvus, Reticulitermes ssp., Termes natalensis, Coptotermes formosanus, thrips (Thysanoptera), such as Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici and other Frankliniella species, Scirtothrips citri, Thrips oryzae, Thrips palmi, Thrips simplex, and Thrips tabaci; ticks and parasitic mites (Parasitiformes): ticks (Ixodida), e.g. Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus, Rhiphicephalus sanguineus, Dermacentor andersoni, Dermacentor variabilis, Amblyomma americanum, Ambryomma maculatum, Ornithodorus hermsi, Ornithodorus turicata and parasitic mites (Mesostigmata), e.g. Ornithonyssus bacoti and Dermanyssus gallinae, true bugs (Hemiptera), e.g. Cimex lectularius, Cimex hemipterus, Reduvius senilis, Triatoma spp., Rhodnius prolixus, and Arilus critatus, Arachnoidea, such as arachnids (Acarina), for example of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Latrodectus mactans, Loxosceles reclusa, Ornithodorus moubata, Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae species such as Aculus schlechtendali, Phyllocoptrata oleivora and Eriophyes sheldoni, Tarsonemidae species such as Phytonemus pallidus and Polyphagotarsonemus latus, Tenuipalpidae species such as Brevipalpus phoenicis; Tetranychidae species such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri, and Oligonychus pratensis, Earwigs (Dermaptera), e.g. forficula auricularia;

Moreover, the crystalline modification I is especially useful for the control of crop pests, in particular of the Coleoptera, Lepidoptera and Acarina orders.

Moreover, the crystalline modification I is especially useful for the control of non-crop pests (household, turf, ornamental). Non-crop pests are pests of the classes Chilopoda and Diplopoda and of the orders Isoptera, Diptera, Blattaria (Blattodea), Dermaptera, Hemiptera, Hymenoptera, Orthoptera, Siphonaptera, Thysanura, Phthiraptera, and Acarina.

For use according to the present invention, the crystalline modification I can be converted into the customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules. The use form depends on the particular intended purpose; in each case, it should ensure a fine and even distribution of the compound according to the invention.

The formulations are prepared in a known manner (see e.g. for review U.S. Pat. No. 3,060,084, EP-A 707 445 (for liquid concentrates), Browning, “Agglomeration”, Chemical Engineering, Dec. 4, 1967, 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and et seq. WO 91/13546, U.S. Pat. No. 4,172,714, U.S. Pat. No. 4,144,050, U.S. Pat. No. 3,920,442, U.S. Pat. No. 5,180,587, U.S. Pat. No. 5,232,701, U.S. Pat. No. 5,208,030, GB 2,095,558, U.S. Pat. No. 3,299,566, Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989 and Mollet, H., Grubemann, A., Formulation technology, Wiley VCH Verlag GmbH, Weinheim (Germany), 2001, 2. D. A. Knowles, Chemistry and Technology of Agrochemical Formulations, Kluwer Academic Publishers, Dordrecht, 1998 (ISBN 0-7514-0443-8), for example by extending the active compound with auxiliaries suitable for the formulation of agrochemicals, such as solvents and/or carriers, if desired surfactants (e.g. adjuvans, emulsifiers, dispersing agents), preservatives, antifoaming agents, anti-freezing agents, for seed treatment formulations also optionally colorants and/or binders and/or gelling agents.

Examples of suitable solvents are water, aromatic solvents (for example Solvesso products, xylene), paraffins (for example mineral oil fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexanone, gamma-butyrolactone), pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols, fatty acid dimethylamides, fatty acids and fatty acid esters. In principle, solvent mixtures may also be used.

Examples of suitable carriers are ground natural minerals (for example kaolins, clays, talc, chalk) and ground synthetic minerals (for example highly disperse silica, silicates).

Suitable surfactants used are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ether, tristearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignosulfite waste liquors and methylcellulose.

Substances which are suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, highly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone or water.

Also anti-freezing agents such as glycerin, ethylene glycol, propylene glycol and bactericides can be added to the formulation.

Suitable antifoaming agents are for example antifoaming agents based on silicon or magnesium stearate,

Suitable preservatives are for example Dichlorophen and enzylalkoholhemiformal.

Seed Treatment formulations may additionally comprise binders and optionally colorants.

Binders can be added to improve the adhesion of the active materials on the seeds after treatment. Suitable binders are block copolymers EO/PO surfactants but also polyvinylalcoholsl, polyvinylpyrrolidones, polyacrylates, polymethacrylates, polybutenes, polyisobutylenes, polystyrene, polyethyleneamines, polyethyleneamides, polyethyleneimines (Lupasol®, Polymin®), polyethers, polyurethans, polyvinylacetate, tylose and copolymers derived from these polymers.

Optionally, also colorants can be included in the formulation. Suitable colorants or dyes for seed treatment formulations are Rhodamin B, C.I. Pigment Red 112, C.I. Solvent Red 1, pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1, pigment blue 80, pigment yellow 1, pigment yellow 13, pigment red 112, pigment red 48:2, pigment red 48:1, pigment red 57:1, pigment red 53:1, pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51, acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.

Examples of a gelling agent is carrageen (Satiagel®).

Powders, materials for spreading and dustable products can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.

Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active compounds to solid carriers.

Examples of solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.

In general, the formulations comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active compound(s). In this case, the active compound(s) are employed in a purity of from 90% to 100% by weight, preferably 95% to 100% by weight (according to NMR spectrum).

For seed treatment purposes, the respective formulations can be diluted 2-10 fold leading to concentrations in the ready to use preparations of 0.01 to 60% by weight active compound by weight, preferably 0.1 to 40% by weight.

The crystalline modification I can be used as such, in the form of their formulations or the use forms prepared therefrom, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dustable products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading or pouring. The use forms depend entirely on the intended purposes; they are intended to ensure in each case the finest possible distribution of the active compound(s) according to the invention.

Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier. However, it is also possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.

The active compound concentrations in the ready-to-use preparations can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1% per weight.

The active compound(s) may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply formulations comprising over 95% by weight of active compound, or even to apply the active compound without additives.

The following are examples of formulations: 1. Products for dilution with water for foliar applications. For seed treatment purposes, such products may be applied to the seed diluted or undiluted.

A) Water-Soluble Concentrates (SL, LS)

10 parts by weight of the active compound(s) are dissolved in 90 parts by weight of water or a water-soluble solvent. As an alternative, wetters or other auxiliaries are added. The active compound(s) dissolves upon dilution with water, whereby a formulation with 10% (w/w) of active compound(s) is obtained.

B) Dispersible Concentrates (DC)

20 parts by weight of the active compound(s) are dissolved in 70 parts by weight of cyclohexanone with addition of 10 parts by weight of a dispersant, for example polyvinylpyrrolidone. Dilution with water gives a dispersion, whereby a formulation with 20% (w/w) of active compound(s) is obtained.

C) Emulsifiable Concentrates (EC)

15 parts by weight of the active compound(s) are dissolved in 80 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution with water gives an emulsion, whereby a formulation with 15% (w/w) of active compound(s) is obtained.

D) Emulsions (EW, EO, ES)

25 parts by weight of the active compound(s) are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is introduced into 30 parts by weight of water by means of an emulsifier machine (e.g. Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion, whereby a formulation with 25% (w/w) of active compound(s) is obtained.

E) Suspensions (SC, OD, FS)

In an agitated ball mill, 20 parts by weight of the active compound(s) are comminuted with addition of 10 parts by weight of dispersants, wetters and 70 parts by weight of water or of an organic solvent to give a fine active compound(s) suspension. Dilution with water gives a stable suspension of the active compound(s), whereby a formulation with 20% (w/w) of active compound(s) is obtained.

F) Water-Dispersible Granules and Water-Soluble Granules (WG, SG)

50 parts by weight of the active compound(s) are ground finely with addition of 50 parts by weight of dispersants and wetters and made as water-dispersible or water-soluble granules by means of technical appliances (for example extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active compound(s), whereby a formulation with 50% (w/w) of active compound(s) is obtained.

G) Water-Dispersible Powders and Water-Soluble Powders (WP, SP, SS, WS)

75 parts by weight of the active compound(s) are ground in a rotor-stator mill with addition of 25 parts by weight of dispersants, wetters and silica gel. Dilution with water gives a stable dispersion or solution of the active compound(s), whereby a formulation with 75% (w/w) of active compound(s) is obtained.

H) Gel-Formulation (GF) (for Seed Treatment Purposes Only)

In an agitated ball mill, 20 parts by weight of the active compound(s) are comminuted with addition of 10 parts by weight of dispersants, 1 part by weight of a gelling agent/wetters and 70 parts by weight of water or of an organic solvent to give a fine active compound(s) suspension. Dilution with water gives a stable suspension of the active compound(s), whereby a formulation with 20% (w/w) of active compound(s) is obtained.

2. Products to be Applied Undiluted for Foliar Applications. For Seed Treatment Purposes, Such Products May be Applied to the Seed Diluted.

I) Dustable Powders (DP, DS)

5 parts by weight of the active compound(s) are ground finely and mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dustable product having 5% (w/w) of active compound(s)

J) Granules (GR, FG, GG, MG)

0.5 part by weight of the active compound(s) is ground finely and associated with 95.5 parts by weight of carriers, whereby a formulation with 0.5% (w/w) of active compound(s) is obtained. Current methods are extrusion, spray-drying or the fluidized bed. This gives granules to be applied undiluted for foliar use.

K) ULV Solutions (UL)

10 parts by weight of the active compound(s) are dissolved in 90 parts by weight of an organic solvent, for example xylene. This gives a product having 10% (w/w) of active compound(s), which is applied undiluted for foliar use.

Conventional seed treatment formulations include for example flowable concentrates FS, solutions LS, powders for dry treatment DS, water dispersible powders for slurry treatment WS, water-soluble powders SS and emulsion ES and EC and gel formulation GF. These formulation can be applied to the seed diluted or undiluted. Application to the seeds is carried out before sowing, either directly on the seeds.

In a preferred embodiment a FS formulation is used for seed treatment. Typically, a FS formulation may comprise 1-800 g/l of active ingredient, 1-200 g/l surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.

The invention relates in particular to pesticidal or parasiticidal compositions in the form of an aqueous suspension concentrate (SC). Such suspension concentrates comprise the crystalline modification I in a finely divided particulate form, where the particles of the crystalline modification I are suspended in an aqueous medium. The size of the active compound particles, i.e. the size which is not exceeded by 90% by weight of the active compound particles, is typically below 30 μm, in particular below 20 μm. Advantageously, at least 40% by weight and in particular at least 60% by weight of the particles in the SCs according to the invention have diameters below 2 μm.

In addition to the active compound, suspension concentrates typically comprise surfactants, and also, if appropriate, antifoam agents, thickeners, antifreeze agents, stabilizers (biocides), agents for adjusting the pH and anticaking agents.

In such SCs, the amount of active compound, i.e. the total amount of the crystalline modification I and, if appropriate, further active compounds is usually in the range from 10 to 70% by weight, in particular in the range from 20 to 50% by weight, based on the total weight of the suspension concentrate.

Preferred surfactants are anionic and nonionic surfactants. The amount of surfactants will generally be from 0.5 to 20% by weight, in particular from 1 to 15% by weight and particularly preferably from 1 to 10% by weight, based on the total weight of the SCs according to the invention. Preferably, the surfactants comprise at least one anionic surfactant and at least one nonionic surfactant, the ratio of anionic to nonionic surfactant typically being in the range from 10:1 to 1:10.

Examples of anionic surfactants include alkylaryl sulfonates, phenyl sulfonates, alkyl sulfates, alkyl sulfonates, alkyl ether sulfates, alkylaryl ether sulfates, alkyl polyglycol ether phosphates, polyaryl phenyl ether phosphates, alkyl sulfosuccinates, olefin sulfonates, paraffin sulfonates, petroleum sulfonates, taurides, sarcosides, fatty acids, alkylnaphthalenesulfonic acids, naphthalenesulfonic acids, lignosulfonic acids, condensates of sulfonated naphthalenes with formaldehyde or with formaldehyde and phenol and, if appropriate, urea, and also condensates of phenolsulfonic acid, formaldehyde and urea, lignosulfite waste liquors and lignosulfonates, alkyl phosphates, alkylaryl phosphates, for example tristyryl phosphates, and also polycarboxylates, such as, for example, polyacrylates, maleic anhydride/olefin copolymers (for example Sokalan® CP9, BASF), including the alkali metal, alkaline earth metal, ammonium and amine salts of the substances mentioned above. Preferred anionic surfactants are those which carry at least one sulfonate group, and in particular their alkali metal and their ammonium salts.

Examples of nonionic surfactants comprise alkylphenol alkoxylates, alcohol alkoxylates, fatty amine alkoxylates, polyoxyethylene glycerol fatty acid esters, castor oil alkoxylates, fatty acid alkoxylates, fatty amide alkoxylates, fatty polydiethanolamides, lanolin ethoxylates, fatty acid polyglycol esters, isotridecyl alcohol, fatty amides, methylcellulose, fatty acid esters, alkyl polyglycosides, glycerol fatty acid esters, polyethylene glycol, polypropylene glycol, polyethylene glycol/polypropylene glycol block copolymers, polyethylene glycol alkyl ethers, polypropylene glycol alkyl ethers, polyethylene glycol/polypropylene glycol ether block copolymers (polyethylene oxide/polypropylene oxide block copolymers) and mixtures thereof. Preferred nonionic surfactants are fatty alcohol ethoxylates, alkyl polyglycosides, glycerol fatty acid esters, castor oil alkoxylates, fatty acid alkoxylates, fatty amide alkoxylates, lanolin ethoxylates, fatty acid polyglycol esters and ethylene oxide/propylene oxide block copolymers and mixtures thereof.

In particular, the SCs according to the invention comprise at least one surfactant which improves wetting of the plant parts by the aqueous application form (wetting agent) and at least one surfactant which stabilizes the dispersion of the active compound particles in the SC (dispersant). The amount of wetting agent is typically in the range from 0.5 to 10% by weight, in particular from 0.5 to 5% by weight and especially from 0.5 to 3% by weight, based on the total weight of the SC. The amount of dispersant is typically from 0.5 to 10% by weight and in particular from 0.5 to 5% by weight, based on the total weight of the SC.

Preferred wetting agents are of anionic or nonionic nature and selected, for example, from naphthalenesulfonic acids including their alkali metal, alkaline earth metal, ammonium and amine salts, furthermore fatty alcohol ethoxylates, alkyl polyglycosides, glycerol fatty acid esters, castor oil alkoxylates, fatty acid alkoxylates, fatty amide alkoxylates, fatty polydiethanolamides, lanolin ethoxylates and fatty acid polyglycol esters.

Preferred dispersants are of anionic or nonionic nature and selected, for example, from polyethylene glycol/polypropylene glycol block copolymers, polyethylene glycol alkyl ethers, polypropylene glycol alkyl ethers, polyethylene glycol/polypropylene glycol ether block copolymers, alkylaryl phosphates, for example tristyryl phosphates, lignosulfonic acids, condensates of sulfonated naphthalenes with formaldehyde or with formaldehyde and phenol and, if appropriate, urea, and also condensates of phenolsulfonic acid, formaldehyde and urea, lignosulfite waste liquors and lignosulfonates, polycarboxylates, such as, for example, polyacrylates, maleic anhydride/olefin copolymers (for example Sokalan® CP9, BASF), including the alkali metal, alkaline earth metal, ammonium and amine salts of the substances mentioned above.

Viscosity-modifying additives (thickeners) suitable for the SCs according to the invention are in particular compounds which bestow upon the formulation pseudoplastic flow properties, i.e. high viscosity in the resting state and low viscosity in the agitated state. Suitable are, in principle, all compounds used for this purpose in suspension concentrates. Mention may be made, for example, of inorganic substances, such as bentonites or attapulgites (for example Attaclay® from Engelhardt), and organic substances, such as polysaccharides and heteropolysaccharides, such as xanthan gum such as sold under the trademarks Kelzan® from Kelco, Rhodopol® 23 from Rhone Poulenc or Veegum® from R.T. Vanderbilt, and preference is given to using xanthan gum. Frequently, the amount of viscosity-modifying additives is from 0.1 to 5% by weight, based on the total weight of the SC.

Antifoam agents suitable for the SCs according to the invention are, for example, silicone emulsions known for this purpose (Silikon® SRE, from Wacker, or Rhodorsil® from Rhodia), long-chain alcohols, fatty acids, defoamers of the type of aqueous wax dispersions, solid defoamers (so-called Compounds), organofluorine compounds and mixtures thereof. The amount of antifoam agent is typically from 0.1 to 1% by weight, based on the total weight of the SC.

Bactericides may be added for stabilizing the suspension concentrates according to the invention. Suitable bactericides are those based on isothiazolones, for example Proxel® from ICI or Acticide® RS from Thor Chemie or Kathon® MK from Rohm & Haas. The amount of bactericides is typically from 0.05 to 0.5% by weight, based on the total weight of the SC.

Suitable antifreeze agents are liquid polyols, for example ethylene glycol, propylene glycol or glycerol. The amount of antifreeze agents is generally from 1 to 20% by weight, in particular from 5 to 10% by weight, based on the total weight of the suspension concentrate.

If appropriate, the SCs according to the invention may comprise buffers for regulating the pH. Examples of buffers are alkali metal salts of weak inorganic or organic acids, such as, for example, phosphoric acid, boric acid, acetic acid, propionic acid, citric acid, fumaric acid, tartaric acid, oxalic acid and succinic acid.

The invention relates in particular to pesticidal or parasiticidal compositions in the form of water-dispersible granules (WG) or a water dispersible powder (WP). Such formulations comprise the crystalline modification I in a finely divided particulate form, where the particles of the crystalline modification I are homogenized in a solid or powder form. The size of the active compound particles, i.e. the size which is not exceeded by 90% by weight of the active compound particles, is typically below 30 μm, in particular below 20 μm. Advantageously, at least 40% by weight and in particular at least 60% by weight of the particles in the WGs or WPs according to the invention have diameters below 5 μm.

In addition to the active compound, water-dispersible powders and water dispersible granules typically comprise surfactants, and also, if appropriate, antifoam agents, fillers, binders, and anticaking agents.

In such WGs and WPs, the amount of active compound, i.e. the total amount of the crystalline modification I and, if appropriate, further active compounds is usually in the range from 10 to 90% by weight, in particular in the range from 20 to 75% by weight, based on the total weight of the WG/WP.

Preferred surfactants are anionic and nonionic surfactants. The amount of surfactants will generally be from 0.5 to 20% by weight, in particular from 1 to 15% by weight and particularly preferably from 1 to 10% by weight, based on the total weight of the WGs or WPs according to the invention. Preferably, the surfactants comprise at least one anionic surfactant and at least one nonionic surfactant, the ratio of anionic to nonionic surfactant typically being in the range from 10:1 to 1:10.

Examples of anionic surfactants include alkylaryl sulfonates, phenyl sulfonates, alkyl sulfates, alkyl sulfonates, alkyl ether sulfates, alkylaryl ether sulfates, alkyl polyglycol ether phosphates, polyaryl phenyl ether phosphates, alkyl sulfosuccinates, olefin sulfonates, paraffin sulfonates, petroleum sulfonates, taurides, sarcosides, fatty acids, alkylnaphthalenesulfonic acids, naphthalenesulfonic acids, lignosulfonic acids, condensates of sulfonated naphthalenes with formaldehyde or with formaldehyde and phenol and, if appropriate, urea, and also condensates of phenolsulfonic acid, formaldehyde and urea, lignosulfite waste liquors and lignosulfonates, alkyl phosphates, alkylaryl phosphates, for example tristyryl phosphates, and also polycarboxylates, such as, for example, polyacrylates, maleic anhydride/olefin copolymers (for example Sokalan® CP9, BASF), including the alkali metal, alkaline earth metal, ammonium and amine salts of the substances mentioned above. Preferred anionic surfactants are those which carry at least one sulfonate group, and in particular their alkali metal and their ammonium salts.

Examples of nonionic surfactants comprise alkylphenol alkoxylates, alcohol alkoxylates, fatty amine alkoxylates, polyoxyethylene glycerol fatty acid esters, castor oil alkoxylates, fatty acid alkoxylates, fatty amide alkoxylates, fatty polydiethanolamides, lanolin ethoxylates, fatty acid polyglycol esters, isotridecyl alcohol, fatty amides, methylcellulose, fatty acid esters, alkyl polyglycosides, glycerol fatty acid esters, polyethylene glycol, polypropylene glycol, polyethylene glycol/polypropylene glycol block copolymers, polyethylene glycol alkyl ethers, polypropylene glycol alkyl ethers, polyethylene glycol/polypropylene glycol ether block copolymers (polyethylene oxide/polypropylene oxide block copolymers) and mixtures thereof. Preferred nonionic surfactants are fatty alcohol ethoxylates, alkyl polyglycosides, glycerol fatty acid esters, castor oil alkoxylates, fatty acid alkoxylates, fatty amide alkoxylates, lanolin ethoxylates, fatty acid polyglycol esters and ethylene oxide/propylene oxide block copolymers and mixtures thereof.

In particular, the WGs or WPs according to the invention comprise at least one surfactant which improves wetting of the formulation by the aqueous application form (wetting agent) and at least one surfactant which allows dispersion of the active compound particles in aqueous dilutions. The amount of wetting agent is typically in the range from 0.5 to 10% by weight, in particular from 0.5 to 5% by weight and especially from 0.5 to 3% by weight, based on the total weight of the WG/WP. The amount of dispersant is typically from 0.5 to 10% by weight and in particular from 2.0 to 8% by weight, based on the total weight of the WG/WP.

Preferred wetting agents are of anionic or nonionic nature and selected, for example, from naphthalenesulfonic acids including their alkali metal, alkaline earth metal, ammonium and amine salts, furthermore fatty alcohol ethoxylates, alkyl polyglycosides, glycerol fatty acid esters, castor oil alkoxylates, fatty acid alkoxylates, fatty amide alkoxylates, fatty polydiethanolamides, lanolin ethoxylates and fatty acid polyglycol esters.

Preferred dispersants are of anionic or nonionic nature and selected, for example, from polyethylene glycol/polypropylene glycol block copolymers, polyethylene glycol alkyl ethers, polypropylene glycol alkyl ethers, polyethylene glycol/polypropylene glycol ether block copolymers, alkylaryl phosphates, for example tristyryl phosphates, sodium phosphates, sodium lauryl sulphate, modified cellulose gum, polyvinylpyrrolidinone, lignosulfonic acids, condensates of sulfonated naphthalenes with formaldehyde or with formaldehyde and phenol and, if appropriate, urea, and also condensates of phenolsulfonic acid, formaldehyde and urea, lignosulfite waste liquors and lignosulfonates, polycarboxylates, such as, for example, polyacrylates, maleic anhydride/olefin copolymers (for example Sokalan® CP9, BASF), including the alkali metal, alkaline earth metal, ammonium and amine salts of the substances mentioned above.

Antifoam agents suitable for the WGs or WPs according to the invention are, for example, tallow soap known for this purpose (Agnique Soap L, Foamaster Soap L), long-chain alcohols, fatty acids, organofluorine compounds and mixtures thereof. The amount of antifoam agent is typically from 0.1 to 1% by weight, based on the total weight of the WG/WP.

Fillers, binders, or additional dispersing aids suitable for the WGs and WPs according to the invention typically make up the remainer of the formulation. These typically are for example kaolin or attapulgite clay, fumed or precipitated silica, diatomateous earth, ammonium sulphate, or calcium silicate.

The crystalline modification I is effective through both contact and ingestion.

According to a preferred embodiment of the invention, the crystalline modification I is employed via soil application. Soil application is especially favorable for use against ants, termites, crickets, or cockroaches.

According to another preferred embodiment of the invention, for use against non-crop pests such as ants, termites, wasps, flies, mosquitoes, crickets, locusts, or cockroaches the crystalline modification I is prepared into a bait preparation.

The bait can be a liquid, a solid or a semisolid preparation (e.g. a gel). Solid baits can be formed into various shapes and forms suitable to the respective application e.g. granules, blocks, sticks, disks. Liquid baits can be filled into various devices to ensure proper application, e.g. open containers, spray devices, droplet sources, or evaporation sources. Gels can be based on aqueous or oily matrices and can be formulated to particular necessities in terms of stickiness, moisture retention or aging characteristics.

The bait employed in the composition is a product which is sufficiently attractive to incite insects such as ants, termites, wasps, flies, mosquitoes, crickets etc. or cockroaches to eat it. This attractant may be chosen from feeding stimulants or para and/or sex pheromones. Suitable feeding stimulants are chosen, for example, from animal and/or plant proteins (meat-, fish- or blood meal, insect parts, crickets powder, egg yolk), from fats and oils of animal and/or plant origin, or mono-, oligo- or polyorganosaccharides, especially from sucrose, lactose, fructose, dextrose, glucose, starch, pectin or even molasses or honey, or from salts such as ammonium sulfate, ammonium carbonate or ammonium acetate. Fresh or decaying parts of fruits, crops, plants, animals, insects or specific parts thereof can also serve as a feeding stimulant. Pheromones are known to be more insect specific. Specific pheromones are described in the literature and are known to those skilled in the art.

We have found that the pesticidal mixtures solve the problems of reducing the dosage rate and/or enhancing the spectrum of activity and/or combining knock-down activity with prolonged control and/or to resistance management and/or promoting the health of plants.

Compositions of this invention may also contain other active ingredients, for example other pesticides, insecticides, fungicides, herbicides, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators, safeners and nematicides. These additional ingredients may be used sequentially or in combination with the above-described compositions, if appropriate also added only immediately prior to use (tank mix). For example, the plant(s) may be sprayed with a composition of this invention either before or after being treated with other active ingredients.

It has been found that a mixture of modification I and at least a pesticidal or fungicidal compound as defined below show markedly enhanced action against pests and/or fungi compared to the control rates that are possible with the individual compounds and/or is suitable for improving the health of plants when applied to plants, parts of plants, seeds, or at their locus of growth.

The following list of pesticidal or parasiticidal compounds which can be used together with the crystalline modification I according to the invention is intended to illustrate the possible combinations, but not to impose any limitation:

A.1. Organo(thio)phosphates: acephate, azamethiphos, azinphos-methyl, chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, fenitrothion, fenthion, isoxathion, malathion, methamidophos, methidathion, methyl-parathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phenthoate, phosalone, phosmet, phosphamidon, phorate, phoxim, pirimiphos-methyl, profenofos, prothiofos, sulprophos, tetrachlorvinphos, terbufos, triazophos, trichlorfon; A.2. Carbamates: alanycarb, aldicarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbosulfan, fenoxycarb, furathiocarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb, triazamate; A.3. Pyrethroids: allethrin, bifenthrin, cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, imiprothrin, lambda-cyhalothrin, permethrin, prallethrin, pyrethrin I and II, resmethrin, silafluofen, tau-fluvalinate, tefluthrin, tetramethrin, tralomethrin, transfluthrin, profluthrin, dimefluthrin; A.4. Growth regulators: a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron; buprofezin, diofenolan, hexythiazox, etoxazole, clofentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide, azadirachtin; c) juvenoids: pyriproxyfen, methoprene, fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirotetramat; A.5. Nicotinic receptor agonists/antagonists compounds: clothianidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram, acetamiprid, thiacloprid; the thiazol compound of formula Γ¹

A.6. GABA antagonist compounds: acetoprole, endosulfan, ethiprole, fipronil, vaniliprole, pyrafluprole, pyriprole, 5-Amino-1-(2,6-dichloro-4-trifluoromethyl-phenyl)-4-trifluoromethanesulfinyl-1H-pyrazole-3-carbothioic acid amide of formula Γ²

A.7. Macrocyclic lactone insecticides: abamectin, emamectin, milbemectin, lepimectin, spinosad; A.8. METI I compounds: fenazaquin, pyridaben, tebufenpyrad, tolfenpyrad, flufenerim; A.9. METI II and III compounds: acequinocyl, fluacyprim, hydramethylnon; A.10. Uncoupler compounds: chlorfenapyr; A.11. Oxidative phosphorylation inhibitor compounds: cyhexatin, diafenthiuron, fenbutatin oxide, propargite; A.12. Moulting disruptor compounds: cyromazine; A.13. Mixed Function Oxidase inhibitor compounds: piperonyl butoxide; A.14. Sodium channel blocker compounds: indoxacarb, metaflumizone, A.15. Various: benclothiaz, bifenazate, cartap, flonicamid, pyridalyl, pymetrozine, sulfur, thiocyclam, flubendiamide, cyenopyrafen, flupyrazofos, cyflumetofen, amidoflumet, the anthranilamide compounds of formula Γ³

wherein A1 is CH₃, Cl, Br, I, X is C—H, C—Cl, C—F or N, Y′ is F, Cl, or Br, Y″ is hydrogen, F, Cl, CF₃, B¹ is hydrogen, Cl, Br, I, CN, B² is Cl, Br, CF₃, OCH₂CF₃, OCF₂H, and R^(B) is hydrogen, CH₃ or CH(CH₃)₂, and the malononitrile compounds as described in JP 2002 284608, WO 02/89579, WO 02/90320, WO 02/90321, WO 04/06677, WO 04/20399, JP 2004 99597, WO 05/68423, WO 05/68432, or WO 05/63694, especially the malononitrile compounds CF₂HCF₂CF₂CF₂CH₂C(CN)₂CH₂CH₂CF₃(2-(2,2,3,3,4,4,5,5-octafluoropentyl)-2-(3,3,3-trifluoropropyl)malononitrile), CF₃(CH₂)₂C(CN)₂CH₂(CF₂)₅CF₂H (2-(2,2,3,3,4,4,5,5,6,6,7,7-Dodecafluoro-heptyl)-2-(3,3,3-trifluoro-propyl)-malononitrile), CF₃(CH₂)₂C(CN)₂(CH₂)₂C(CF₃)₂F (2-(3,4,4,4-Tetrafluoro-3-trifluoromethyl-butyl)-2-(3,3,3-trifluoro-propyl)-malononitrile), CF₃(CH₂)₂C(CN)₂(CH₂)₂(CF₂)₃CF₃(2-(3,3,4,4,5,5,6,6,6-Nonafluoro-hexyl)-2-(3,3,3-trifluoro-propyl)-malononitrile), CF₂H(CF₂)₃CH₂C(CN)₂CH₂(CF₂)₃CF₂H (2,2-Bis-(2,2,3,3,4,4,5,5-octafluoro-pentyl)-malononitrile), CF₃(CH₂)₂C(CN)₂CH₂(CF₂)₃CF₃ (2-(2,2,3,3,4,4,5,5,5-Nonafluoro-pentyl)-2-(3,3,3-trifluoro-propyl)-malononitrile), CF₃(CF₂)₂CH₂C(CN)₂CH₂(CF₂)₃CF₂H (2-(2,2,3,3,4,4,4-Heptafluoro-butyl)-2-(2,2,3,3,4,4,5,5-octafluoro-pentyl)-malononitrile) and CF₃CF₂CH₂C(CN)₂CH₂(CF₂)₃CF₂H (2-(2,2,3,3,4,4,5,5-Octafluoro-pentyl)-2-(2,2,3,3,3-pentafluoro-propyl)-malononitrile).

The commercially available compounds of the group A may be found in The Pesticide Manual, 13^(th) Edition, British Crop Protection Council (2003) among other publications. Thioamides of formula Γ² and their preparation have been described in WO 98/28279. Lepimectin is known from Agro Project, PJB Publications Ltd, November 2004. Benclothiaz and its preparation have been described in EP-A1 454621. Methidathion and Paraoxon and their preparation have been described in Farm Chemicals Handbook, Volume 88, Meister Publishing Company, 2001. Acetoprole and its preparation have been described in WO 98/28277. Metaflumizone and its preparation have been described in EP-A1 462 456. Flupyrazofos has been described in Pesticide Science 54, 1988, p. 237-243 and in U.S. Pat. No. 4,822,779. Pyrafluprole and its preparation have been described in JP 2002193709 and in WO 01/00614. Pyriprole and its preparation have been described in WO 98/45274 and in U.S. Pat. No. 6,335,357. Amidoflumet and its preparation have been described in U.S. Pat. No. 6,221,890 and in JP 21010907. Flufenerim and its preparation have been described in WO 03/007717 and in WO 03/007718. Cyflumetofen and its preparation have been described in WO 04/080180. Anthranilamides of formula Γ³ and their preparation have been described in WO 01/70671; WO 02/48137; WO 03/24222, WO 03/15518, WO 04/67528; WO 04/33468; and WO 05/118552. The malononitrile compounds CF₂HCF₂CF₂CF₂CH₂C(CN)₂CH₂CH₂CF₃ (2-(2,2,3,3,4,4,5,5-octafluoropentyl)-2-(3,3,3-trifluoropropyl)malononitrile), CF₃(CH₂)₂C(CN)₂CH₂(CF₂)₅CF₂H (2-(2,2,3,3,4,4,5,5,6,6,7,7-Dodecafluoro-heptyl)-2-(3,3,3-trifluoro-propyl)-malononitrile), CF₃(CH₂)₂C(CN)₂(CH₂)₂C(CF₃)₂F (2-(3,4,4,4-Tetrafluoro-3-trifluoromethyl-butyl)-2-(3,3,3-trifluoro-propyl)-malononitrile), CF₃(CH₂)₂C(CN)₂(CH₂)₂(CF₂)₃CF₃ (2-(3,3,4,4,5,5,6,6,6-Nonafluoro-hexyl)-2-(3,3,3-trifluoro-propyl)-malononitrile), CF₂H(CF₂)₃CH₂C(CN)₂CH₂(CF₂)₃CF₂H (2,2-Bis-(2,2,3,3,4,4,5,5-octafluoro-pentyl)-malononitrile), CF₃(CH₂)₂C(CN)₂CH₂(CF₂)₃CF₃ (2-(2,2,3,3,4,4,5,5,5-Nonafluoro-pentyl)-2-(3,3,3-trifluoro-propyl)-malononitrile), CF₃(CF₂)₂CH₂C(CN)₂CH₂(CF₂)₃CF₂H (2-(2,2,3,3,4,4,4-Heptafluoro-butyl)-2-(2,2,3,3,4,4,5,5-octafluoro-pentyl)-malononitrile) and CF₃CF₂CH₂C(CN)₂CH₂(CF₂)₃CF₂H (2-(2,2,3,3,4,4,5,5-Octafluoro-pentyl)-2-(2,2,3,3,3-pentafluoro-propyl)-malononitrile) have been described in WO 05/63694.

The following list of fungicidal compounds which can be used together with the crystalline modification I according to the invention is intended to illustrate the possible combinations, but not to impose any limitation:

Preferred are the binary mixtures containing modification I as compound I.

Preferred are the tertiary mixtures containing modification I as compound I, a compound IIA, and a compound IIB.

Preferred are the quaternary mixtures containing modification I as compound I, a compound IIA, and two compounds IIB1 and IIB2, resp.

Especially preferred are binary mixtures containing modification I as compound I and a fungicidal compound IIA selected from the list comprising azoles: cyproconazole, difenoconazole, epoxiconazole, fenbuconazole, fluquinconazole, flutriafol, hexaconazole, ipconazole, metconazole, propiconazole, prothioconazole, tebuconazole, tetraconazole, triadimenol, triadimefon, triticonazole, cyazofamid, imazalil, prochloraz, triflumizol, benomyl, carbendazim, thiabendazole, ethaboxam, and hymexazole.

Especially preferred are binary mixtures containing modification I as compound I and a fungicidal compound IIA selected from the list comprising strobilurins: azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, metominostrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, methyl (2-chloro-5-[1-(3-methylbenzyloxyimino)ethyl]benzyl)carbamate, methyl (2-chloro-5-[1-(6-methylpyridin-2-ylmethoxyimino)ethyl]benzyl)carbamate, and methyl 2-(ortho-((2,5-dimethylphenyloxy-methylene)phenyl)-3-methoxyacrylate;

Especially preferred are binary mixtures containing modification I as compound I and a fungicidal compound IIA selected from the list comprising carboxamides: boscalid, carboxin, benalaxyl, fenhexamid, flutolanil, furametpyr, metalaxyl, mefenoxam (metalaxyl-M), ofurace, oxadixyl, oxycarboxin, penthiopyrad, thifluzamide, tiadinil, dimethomorph, fluopicolide (picobenzamid), diclocymet, N-(4′-bromobiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide, N-(4′-trifluoromethylbiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide, N-(4′-chloro-3′-fluorobiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide, N-(3′,4′-dichloro-4-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methylpyrazole-4-carboxamide, N-(3′,4′-dichloro-5-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methylpyrazole-4-carboxamide; 3,4-dichloro-N-(2-cyanophenyl)isothiazol-5-carboxamide; N-(2′,4′-difluorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide; N-(2′,4′-dichlorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide; N-(2′,4′-difluorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide; N-(2′,4′-dichloro-biphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide; N-(2′,5′-difluorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide; N-(2′,5′-dichlorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide; N-(2′,5′-difluorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide; N-(2′,5′-dichlorobiphenyl-2-yl)-3-di-fluoromethyl-1-methyl-1H-pyrazole-4-carboxamide; N-(3′,5′-difluoro-biphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide; N-(3′,5′-dichlorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide, N-(3′,5′-difluorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide; N-(3′,5′-dichlorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide; N-(3′-fluorobiphenyl-2-yl)-1-methyl-3-trifluoro-methyl-1H-pyrazole-4-carboxamide, N-(3′-chlorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide; N-(3′-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide, N-(3′-chlorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide; N-(2′-fluorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide; N-(2′-chlorobiphenyl-2-yl)-1-methyl-3-trifluoro-methyl-1H-pyrazole-4-carboxamide; N-(2′-fluorobiphenyl-2-yl)-3-difluoro-methyl-1-methyl-1H-pyrazole-4-carboxamide; N-(2′-chlorbiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide; N-(2′-fluoro-4′-chloro-5′-methylbiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carbox-amide; N-(3′,4′,5′-trifluorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide; N-(3′,4′,5′-trifluorobiphenyl-2-yl)-1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxamide; N-(2′,4′,5′-trifluorobiphenyl-2-yl)-1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxamide; N-(3′,4′,5′-tri-fluorobiphenyl-2-yl)-3-chlorofluoromethyl-1-methyl-1H-pyrazole-4-carbox-amide; N-[2-(1,1,2,3,3,3-hexa-fluoropropoxy)phenyl]-1-methyl-3-trifluoro-methyl-1H-pyrazole-4-carboxamide; N-[2-(1,1,2,3,3,3-hexafluor-opropoxy)-phenyl]-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide, N-[2-(2-chloro-1,1,2-trifluoroethoxy)phenyl]-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide; N-[2-(2-chlor-1,1,2-trifluoroethoxy)phenyl]-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide; N-[2-(1,1,2,2-tetra-fluoroethoxy)phenyl]-3-difluoromethyl-1-methyl-1H-pyrazole-4-carbox-amide; N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-1-methyl-3-trifluoro-methyl-1H-pyrazole-4-carboxamide; N-(4′-(trifluoromethylthio)biphenyl-2-yl)-3-di-fluoromethyl-1-methyl-1H-pyrazole-4-carboxamide; N-(4′-(trifluoromethyl-thio)biphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide; and 5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxylic acid [2-(1,2-dimethyl-propyl)-phenyl]-amide.

Especially preferred are binary mixtures containing modification I as compound I and a fungicidal compound IIA selected from the list comprising heterocylic compounds: pyrimethanil, fenpiclonil, fludioxonil, aldimorph, dodemorph, fenpropimorph, tridemorph, iprodione, procymidone, famoxadone, fenamidone, octhilinone, probenazole, diclomezine, pyroquilon, proquinazid, tricyclazole, captafol, captan, dazomet, fenoxanil, quinoxyfen, 5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]-triazolo[1,5-a]pyrimidine, 6-(3,4-dichloro-phenyl)-5-methyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-yl-amine, 6-(4-tert-butylphenyl)-5-methyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine, 5-methyl-6-(3,5,5-trimethyl-hexyl)-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine, 5-methyl-6-octyl-[1,2,4]triazolo[1,5-a]pyrimi-dine-7-ylamine, 6-methyl-5-octyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine, 6-ethyl-5-octyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine, 5-ethyl-6-octyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine, 5-ethyl-6-(3,5,5-trimethyl-hex-yl)-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine, 6-octyl-5-propyl-[1,2,4]tri-azolo[1,5-a]pyrimidine-7-ylamine, 5-methoxymethyl-6-octyl-[1,2,4]tri-azolo[1,5-a]pyrimidine-7-ylamine, 6-octyl-5-trifluoromethyl-[1,2,4]tri-azolo[1,5-a]pyrimidine-7-ylamine, and 5-trifluoro-methyl-6-(3,5,5-trimethyl-hexyl)-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine.

Especially preferred are binary mixtures containing modification I as compound I and a fungicidal compound IIA selected from the list comprising carbamates: mancozeb, maneb, metam, metiram, ferbam, propineb, thiram, zineb, ziram; diethofencarb, iprovalicarb, propamocarb, and methyl 3-(4-chlorophenyl)-3-(2-isopropoxycarbonyl-amino-3-methylbutyrylamino)propanoate.

Especially preferred are binary mixtures containing modification I as compound I and a fungicidal compound IIA selected from the list comprising: guazatine; streptomycin, validamycin A; binapacryl, dinocap, dinobuton; dithianon, isoprothiolane; fentin salts, such as fentin-acetate; edifenphos, iprobenfos, fosetyl, pyrazophos, chlorothalonil, dichlofluanid, flusulfamide, phthalide, quintozene, thiophanate-methyl, tolylfluanid; copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur; cyflufenamid, cymoxanil, dimethirimol, ethirimol, furalaxyl, metrafenone, and spiroxamine.

The active compounds IIA mentioned above, their preparation and their action against harmful fungi are generally known (cf.: http://www.hclrss.demon.co.uk/index.html); they are commercially available. The compounds named according to IUPAC, their preparation and their fungicidal activity are likewise known from EP-A 12 01 648; EP-A 226 917; WO 98/46608; WO 99/24413; WO 2004/049804; WO 2003/066609; WO 2003/053145; WO 2003/14103; EP-A 10 35 122; EP-A 10 28 125; EP-A 71 792; EP-A 141 317; WO 2003/009687; WO 05/087771; WO 2005/087772; WO 2005/087773; WO 2006/087325; WO 2006/087325; WO 2006/092428; WO 2006/092428; WO 2006/087343; WO 2001/42223; WO 2005/34628; WO 2005/123689; WO 2005/123690; WO 2006/120219; PCT/EP2006/064991; WO 2007/017450, and EP Application No. 06123463.9

With respect to their intended use, the following tertiary and quaternary mixtures of modification I as compound I are especially preferred:

Table1

Mixtures wherein compound IIA is trifloxystrobin, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table2

Mixtures wherein compound IIA is azoxystrobin, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table3

Mixtures wherein compound IIA is pyraclostrobin, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table4

Mixtures wherein compound IIA is boscalid, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table5

Mixtures wherein compound IIA is metalaxyl, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table6

Mixtures wherein compound IIA is metalaxyl-M, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table7

Mixtures wherein compound IIA is cyproconazole, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table8

Mixtures wherein compound IIA is epoxiconazole, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table9

Mixtures wherein compound IIA is fenbuconazole, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table10

Mixtures wherein compound IIA is fluquinconazole, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table11

Mixtures wherein compound IIA is flutriafol, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table12

Mixtures wherein compound IIA is ipconazole, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table13

Mixtures wherein compound IIA is metconazole, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table14

Mixtures wherein compound IIA is propiconazole, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table15

Mixtures wherein compound IIA is prothioconazole, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table16

Mixtures wherein compound IIA is tebuconazole, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table17

Mixtures wherein compound IIA is triadimenol, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table18

Mixtures wherein compound IIA is triticonazole, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table19

Mixtures wherein compound IIA is imazalil, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table20

Mixtures wherein compound IIA is prochloraz, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table21

Mixtures wherein compound IIA is carbendazim, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table22

Mixtures wherein compound IIA is thiabendazole, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table23

Mixtures wherein compound IIA is ethaboxam, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table24

Mixtures wherein compound IIA is hymexazole, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table25

Mixtures wherein compound IIA is pyrimethanil, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table26

Mixtures wherein compound IIA is fludioxonil, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table27

Mixtures wherein compound IIA is aldimorph, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table28

Mixtures wherein compound IIA is dodemorph, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table29

Mixtures wherein compound IIA is fenpropimorph, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table30

Mixtures wherein compound IIA is iprodione, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table31

Mixtures wherein compound IIA is captan, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table32

Mixtures wherein compound IIA is fenoxanil, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table33

Mixtures wherein compound IIA is probenazole, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table34

Mixtures wherein compound IIA is mancozeb, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table35

Mixtures wherein compound IIA is metiram, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table36

Mixtures wherein compound IIA is thiram, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table37

Mixtures wherein compound IIA is ziram, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table38

Mixtures wherein compound IIA is guazatin, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table39

Mixtures wherein compound IIA is thiophanate-methyl, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table40

Mixtures wherein compound IIA is chlorothalonil, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table41

Mixtures wherein compound IIA is metrafenone, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

TABLE Q Mixture No. Compound IIB1 Compound IIB2 M-1 azoxystrobin — M-2 azoxystrobin boscalid M-3 azoxystrobin metalaxyl M-4 azoxystrobin cyproconazole M-5 azoxystrobin epoxiconazole M-6 azoxystrobin fenbuconazole M-7 azoxystrobin fluquinconazole M-8 azoxystrobin flutriafol M-9 azoxystrobin ipconazole M-10 azoxystrobin metconazole M-11 azoxystrobin propiconazole M-12 azoxystrobin prothioconazole M-13 azoxystrobin tebuconazole M-14 azoxystrobin triadimenol M-15 azoxystrobin triticonazole M-16 azoxystrobin imazalil M-17 azoxystrobin prochloraz M-18 azoxystrobin carbendazim M-19 azoxystrobin thiabendazole M-20 azoxystrobin ethaboxam M-21 azoxystrobin hymexazole M-22 azoxystrobin pyrimethanil M-23 azoxystrobin fludioxonil M-24 azoxystrobin aldimorph M-25 azoxystrobin dodemorph M-26 azoxystrobin fenpropimorph M-27 azoxystrobin iprodione M-28 azoxystrobin captan M-29 azoxystrobin fenoxanil M-30 azoxystrobin probenazol M-31 azoxystrobin mancozeb M-32 azoxystrobin metiram M-33 azoxystrobin thiram M-34 azoxystrobin ziram M-35 azoxystrobin guazatin M-36 azoxystrobin thiophanate- methyl M-37 azoxystrobin chlorothalonil M-38 azoxystrobin metrafenone M-39 trifloxystrobin — M-40 trifloxystrobin boscalid M-41 trifloxystrobin metalaxyl M-42 trifloxystrobin cyproconazole M-43 trifloxystrobin epoxiconazole M-44 trifloxystrobin fenbuconazole M-45 trifloxystrobin fluquinconazole M-46 trifloxystrobin flutriafol M-47 trifloxystrobin ipconazole M-48 trifloxystrobin metconazole M-49 trifloxystrobin propiconazole M-50 trifloxystrobin prothioconazole M-51 trifloxystrobin tebuconazole M-52 trifloxystrobin triadimenol M-53 trifloxystrobin triticonazole M-54 trifloxystrobin imazalil M-55 trifloxystrobin prochloraz M-56 trifloxystrobin carbendazim M-57 trifloxystrobin thiabendazole M-58 trifloxystrobin ethaboxam M-59 trifloxystrobin hymexazole M-60 trifloxystrobin pyrimethanil M-61 trifloxystrobin fludioxonil M-62 trifloxystrobin aldimorph M-63 trifloxystrobin dodemorph M-64 trifloxystrobin fenpropimorph M-65 trifloxystrobin iprodione M-66 trifloxystrobin captan M-67 trifloxystrobin fenoxanil M-68 trifloxystrobin probenazol M-69 trifloxystrobin mancozeb M-70 trifloxystrobin metiram M-71 trifloxystrobin thiram M-72 trifloxystrobin ziram M-73 trifloxystrobin guazatin M-74 trifloxystrobin thiophanate- methyl M-75 trifloxystrobin chlorothalonil M-76 trifloxystrobin metrafenone M-77 orysastrobin — M-78 orysastrobin boscalid M-79 orysastrobin metalaxyl M-80 orysastrobin cyproconazole M-81 orysastrobin epoxiconazole M-82 orysastrobin fenbuconazole M-83 orysastrobin fluquinconazole M-84 orysastrobin flutriafol M-85 orysastrobin ipconazole M-86 orysastrobin metconazole M-87 orysastrobin propiconazole M-88 orysastrobin prothioconazole M-89 orysastrobin tebuconazole M-90 orysastrobin triadimenol M-91 orysastrobin triticonazole M-92 orysastrobin imazalil M-93 orysastrobin prochloraz M-94 orysastrobin carbendazim M-95 orysastrobin thiabendazole M-96 orysastrobin ethaboxam M-97 orysastrobin hymexazole M-98 orysastrobin pyrimethanil M-99 orysastrobin fludioxonil M-100 orysastrobin aldimorph M-101 orysastrobin dodemorph M-102 orysastrobin fenpropimorph M-103 orysastrobin iprodione M-104 orysastrobin captan M-105 orysastrobin fenoxanil M-106 orysastrobin probenazol M-107 orysastrobin mancozeb M-108 orysastrobin metiram M-109 orysastrobin thiram M-110 orysastrobin ziram M-111 orysastrobin guazatin M-112 orysastrobin thiophanate- methyl M-113 orysastrobin chlorothalonil M-114 orysastrobin metrafenone M-115 pyraclostrobin — M-116 pyraclostrobin boscalid M-117 pyraclostrobin metalaxyl M-118 pyraclostrobin cyproconazole M-119 pyraclostrobin epoxiconazole M-120 pyraclostrobin fenbuconazole M-121 pyraclostrobin fluquinconazole M-122 pyraclostrobin flutriafol M-123 pyraclostrobin ipconazole M-124 pyraclostrobin metconazole M-125 pyraclostrobin propiconazole M-126 pyraclostrobin prothioconazole M-127 pyraclostrobin tebuconazole M-128 pyraclostrobin triadimenol M-129 pyraclostrobin triticonazole M-130 pyraclostrobin imazalil M-131 pyraclostrobin prochloraz M-132 pyraclostrobin carbendazim M-133 pyraclostrobin thiabendazole M-134 pyraclostrobin ethaboxam M-135 pyraclostrobin hymexazole M-136 pyraclostrobin pyrimethanil M-137 pyraclostrobin fludioxonil M-138 pyraclostrobin aldimorph M-139 pyraclostrobin dodemorph M-140 pyraclostrobin fenpropimorph M-141 pyraclostrobin iprodione M-142 pyraclostrobin captan M-143 pyraclostrobin fenoxanil M-144 pyraclostrobin probenazol M-145 pyraclostrobin mancozeb M-146 pyraclostrobin metiram M-147 pyraclostrobin thiram M-148 pyraclostrobin ziram M-149 pyraclostrobin guazatin M-150 pyraclostrobin thiophanate- methyl M-151 pyraclostrobin chlorothalonil M-152 pyraclostrobin metrafenone M-153 boscalid — M-154 boscalid metalaxyl M-155 boscalid cyproconazole M-156 boscalid epoxiconazole M-157 boscalid fenbuconazole M-158 boscalid fluquinconazole M-159 boscalid flutriafol M-160 boscalid ipconazole M-161 boscalid metconazole M-162 boscalid propiconazole M-163 boscalid prothioconazole M-164 boscalid tebuconazole M-165 boscalid triadimenol M-166 boscalid triticonazole M-167 boscalid imazalil M-168 boscalid prochloraz M-169 boscalid carbendazim M-170 boscalid thiabendazole M-171 boscalid ethaboxam M-172 boscalid hymexazole M-173 boscalid pyrimethanil M-174 boscalid fludioxonil M-175 boscalid aldimorph M-176 boscalid dodemorph M-177 boscalid fenpropimorph M-178 boscalid iprodione M-179 boscalid captan M-180 boscalid fenoxanil M-181 boscalid probenazol M-182 boscalid mancozeb M-183 boscalid metiram M-184 boscalid thiram M-185 boscalid ziram M-186 boscalid guazatin M-187 boscalid thiophanate- methyl M-188 boscalid chlorothalonil M-189 boscalid metrafenone M-190 metalaxyl — M-191 metalaxyl cyproconazole M-192 metalaxyl epoxiconazole M-193 metalaxyl fenbuconazole M-194 metalaxyl fluquinconazole M-195 metalaxyl flutriafol M-196 metalaxyl ipconazole M-197 metalaxyl metconazole M-198 metalaxyl propiconazole M-199 metalaxyl prothioconazole M-200 metalaxyl tebuconazole M-201 metalaxyl triadimenol M-202 metalaxyl triticonazole M-203 metalaxyl imazalil M-204 metalaxyl prochloraz M-205 metalaxyl carbendazim M-206 metalaxyl thiabendazole M-207 metalaxyl ethaboxam M-208 metalaxyl hymexazole M-209 metalaxyl pyrimethanil M-210 metalaxyl fludioxonil M-211 metalaxyl aldimorph M-212 metalaxyl dodemorph M-213 metalaxyl fenpropimorph M-214 metalaxyl iprodione M-215 metalaxyl captan M-216 metalaxyl fenoxanil M-217 metalaxyl probenazol M-218 metalaxyl mancozeb M-219 metalaxyl metiram M-220 metalaxyl thiram M-221 metalaxyl ziram M-222 metalaxyl guazatin M-223 metalaxyl thiophanate- methyl M-224 metalaxyl chlorothalonil M-225 metalaxyl metrafenone M-226 cyproconazole — M-227 cyproconazole epoxiconazole M-228 cyproconazole fenbuconazole M-229 cyproconazole fluquinconazole M-230 cyproconazole flutriafol M-231 cyproconazole ipconazole M-232 cyproconazole metconazole M-233 cyproconazole propiconazole M-234 cyproconazole prothioconazole M-235 cyproconazole tebuconazole M-236 cyproconazole triadimenol M-237 cyproconazole triticonazole M-238 cyproconazole imazalil M-239 cyproconazole prochloraz M-240 cyproconazole carbendazim M-241 cyproconazole thiabendazole M-242 cyproconazole ethaboxam M-243 cyproconazole hymexazole M-244 cyproconazole pyrimethanil M-245 cyproconazole fludioxonil M-246 cyproconazole aldimorph M-247 cyproconazole dodemorph M-248 cyproconazole fenpropimorph M-249 cyproconazole iprodione M-250 cyproconazole captan M-251 cyproconazole fenoxanil M-252 cyproconazole probenazol M-253 cyproconazole mancozeb M-254 cyproconazole metiram M-255 cyproconazole thiram M-256 cyproconazole ziram M-257 cyproconazole guazatin M-258 cyproconazole thiophanate- methyl M-259 cyproconazole chlorothalonil M-260 cyproconazole metrafenone M-261 epoxiconazole — M-262 epoxiconazole fenbuconazole M-263 epoxiconazole fluquinconazole M-264 epoxiconazole flutriafol M-265 epoxiconazole ipconazole M-266 epoxiconazole metconazole M-267 epoxiconazole propiconazole M-268 epoxiconazole prothioconazole M-269 epoxiconazole tebuconazole M-270 epoxiconazole triadimenol M-271 epoxiconazole triticonazole M-272 epoxiconazole imazalil M-273 epoxiconazole prochloraz M-274 epoxiconazole carbendazim M-275 epoxiconazole thiabendazole M-276 epoxiconazole ethaboxam M-277 epoxiconazole hymexazole M-278 epoxiconazole pyrimethanil M-279 epoxiconazole fludioxonil M-280 epoxiconazole aldimorph M-281 epoxiconazole dodemorph M-282 epoxiconazole fenpropimorph M-283 epoxiconazole iprodione M-284 epoxiconazole captan M-285 epoxiconazole fenoxanil M-286 epoxiconazole probenazol M-287 epoxiconazole mancozeb M-288 epoxiconazole metiram M-289 epoxiconazole thiram M-290 epoxiconazole ziram M-291 epoxiconazole guazatin M-292 epoxiconazole thiophanate- methyl M-293 epoxiconazole chlorothalonil M-294 epoxiconazole metrafenone M-295 fenbuconazole — M-296 fenbuconazole fluquinconazole M-297 fenbuconazole flutriafol M-298 fenbuconazole ipconazole M-299 fenbuconazole metconazole M-300 fenbuconazole propiconazole M-301 fenbuconazole prothioconazole M-302 fenbuconazole tebuconazole M-303 fenbuconazole triadimenol M-304 fenbuconazole triticonazole M-305 fenbuconazole imazalil M-306 fenbuconazole prochloraz M-307 fenbuconazole carbendazim M-308 fenbuconazole thiabendazole M-309 fenbuconazole ethaboxam M-310 fenbuconazole hymexazole M-311 fenbuconazole pyrimethanil M-312 fenbuconazole fludioxonil M-313 fenbuconazole aldimorph M-314 fenbuconazole dodemorph M-315 fenbuconazole fenpropimorph M-316 fenbuconazole iprodione M-317 fenbuconazole captan M-318 fenbuconazole fenoxanil M-319 fenbuconazole probenazol M-320 fenbuconazole mancozeb M-321 fenbuconazole metiram M-322 fenbuconazole thiram M-323 fenbuconazole ziram M-324 fenbuconazole guazatin M-325 fenbuconazole thiophanate- methyl M-326 fenbuconazole chlorothalonil M-327 fenbuconazole metrafenone M-328 fluquinconazole — M-329 fluquinconazole flutriafol M-330 fluquinconazole ipconazole M-331 fluquinconazole metconazole M-332 fluquinconazole propiconazole M-333 fluquinconazole prothioconazole M-334 fluquinconazole tebuconazole M-335 fluquinconazole triadimenol M-336 fluquinconazole triticonazole M-337 fluquinconazole imazalil M-338 fluquinconazole prochloraz M-339 fluquinconazole carbendazim M-340 fluquinconazole thiabendazole M-341 fluquinconazole ethaboxam M-342 fluquinconazole hymexazole M-343 fluquinconazole pyrimethanil M-344 fluquinconazole fludioxonil M-345 fluquinconazole aldimorph M-346 fluquinconazole dodemorph M-347 fluquinconazole fenpropimorph M-348 fluquinconazole iprodione M-349 fluquinconazole captan M-350 fluquinconazole fenoxanil M-351 fluquinconazole probenazol M-352 fluquinconazole mancozeb M-353 fluquinconazole metiram M-354 fluquinconazole thiram M-355 fluquinconazole ziram M-356 fluquinconazole guazatin M-357 fluquinconazole thiophanate- methyl M-358 fluquinconazole chlorothalonil M-359 fluquinconazole metrafenone M-360 flutriafol — M-361 flutriafol ipconazole M-362 flutriafol metconazole M-363 flutriafol propiconazole M-364 flutriafol prothioconazole M-365 flutriafol tebuconazole M-366 flutriafol triadimenol M-367 flutriafol triticonazole M-368 flutriafol imazalil M-369 flutriafol prochloraz M-370 flutriafol carbendazim M-371 flutriafol thiabendazole M-372 flutriafol ethaboxam M-373 flutriafol hymexazole M-374 flutriafol pyrimethanil M-375 flutriafol fludioxonil M-376 flutriafol aldimorph M-377 flutriafol dodemorph M-378 flutriafol fenpropimorph M-379 flutriafol iprodione M-380 flutriafol captan M-381 flutriafol fenoxanil M-382 flutriafol probenazol M-383 flutriafol mancozeb M-384 flutriafol metiram M-385 flutriafol thiram M-386 flutriafol ziram M-387 flutriafol guazatin M-388 flutriafol thiophanate- methyl M-389 flutriafol chlorothalonil M-390 flutriafol metrafenone M-391 ipconazole — M-392 ipconazole metconazole M-393 ipconazole propiconazole M-394 ipconazole prothioconazole M-395 ipconazole tebuconazole M-396 ipconazole triadimenol M-397 ipconazole triticonazole M-398 ipconazole imazalil M-399 ipconazole prochloraz M-400 ipconazole carbendazim M-401 ipconazole thiabendazole M-402 ipconazole ethaboxam M-403 ipconazole hymexazole M-404 ipconazole pyrimethanil M-405 ipconazole fludioxonil M-406 ipconazole aldimorph M-407 ipconazole dodemorph M-408 ipconazole fenpropimorph M-409 ipconazole iprodione M-410 ipconazole captan M-411 ipconazole fenoxanil M-412 ipconazole probenazol M-413 ipconazole mancozeb M-414 ipconazole metiram M-415 ipconazole thiram M-416 ipconazole ziram M-417 ipconazole guazatin M-418 ipconazole thiophanate- methyl M-419 ipconazole chlorothalonil M-420 ipconazole metrafenone M-421 metconazole — M-422 metconazole propiconazole M-423 metconazole prothioconazole M-424 metconazole tebuconazole M-425 metconazole triadimenol M-426 metconazole triticonazole M-427 metconazole imazalil M-428 metconazole prochloraz M-429 metconazole carbendazim M-430 metconazole thiabendazole M-431 metconazole ethaboxam M-432 metconazole hymexazole M-433 metconazole pyrimethanil M-434 metconazole fludioxonil M-435 metconazole aldimorph M-436 metconazole dodemorph M-437 metconazole fenpropimorph M-438 metconazole iprodione M-439 metconazole captan M-440 metconazole fenoxanil M-441 metconazole probenazol M-442 metconazole mancozeb M-443 metconazole metiram M-444 metconazole thiram M-445 metconazole ziram M-446 metconazole guazatin M-447 metconazole thiophanate- methyl M-448 metconazole chlorothalonil M-449 metconazole metrafenone M-450 propiconazole — M-451 propiconazole prothioconazole M-452 propiconazole tebuconazole M-453 propiconazole triadimenol M-454 propiconazole triticonazole M-455 propiconazole imazalil M-456 propiconazole prochloraz M-457 propiconazole carbendazim M-458 propiconazole thiabendazole M-459 propiconazole ethaboxam M-460 propiconazole hymexazole M-461 propiconazole pyrimethanil M-462 propiconazole fludioxonil M-463 propiconazole aldimorph M-464 propiconazole dodemorph M-465 propiconazole fenpropimorph M-466 propiconazole iprodione M-467 propiconazole captan M-468 propiconazole fenoxanil M-469 propiconazole probenazol M-470 propiconazole mancozeb M-471 propiconazole metiram M-472 propiconazole thiram M-473 propiconazole ziram M-474 propiconazole guazatin M-475 propiconazole thiophanate- methyl M-476 propiconazole chlorothalonil M-477 propiconazole metrafenone M-478 prothioconazole — M-479 prothioconazole tebuconazole M-480 prothioconazole triadimenol M-481 prothioconazole triticonazole M-482 prothioconazole imazalil M-483 prothioconazole prochloraz M-484 prothioconazole carbendazim M-485 prothioconazole thiabendazole M-486 prothioconazole ethaboxam M-487 prothioconazole hymexazole M-488 prothioconazole pyrimethanil M-489 prothioconazole fludioxonil M-490 prothioconazole aldimorph M-491 prothioconazole dodemorph M-492 prothioconazole fenpropimorph M-493 prothioconazole iprodione M-494 prothioconazole captan M-495 prothioconazole fenoxanil M-496 prothioconazole probenazol M-497 prothioconazole mancozeb M-498 prothioconazole metiram M-499 prothioconazole thiram M-500 prothioconazole ziram M-501 prothioconazole guazatin M-502 prothioconazole thiophanate- methyl M-503 prothioconazole chlorothalonil M-504 prothioconazole metrafenone M-505 tebuconazole — M-506 tebuconazole triadimenol M-507 tebuconazole triticonazole M-508 tebuconazole imazalil M-509 tebuconazole prochloraz M-510 tebuconazole carbendazim M-511 tebuconazole thiabendazole M-512 tebuconazole ethaboxam M-513 tebuconazole hymexazole M-514 tebuconazole pyrimethanil M-515 tebuconazole fludioxonil M-516 tebuconazole aldimorph M-517 tebuconazole dodemorph M-518 tebuconazole fenpropimorph M-519 tebuconazole iprodione M-520 tebuconazole captan M-521 tebuconazole fenoxanil M-522 tebuconazole probenazol M-523 tebuconazole mancozeb M-524 tebuconazole metiram M-525 tebuconazole thiram M-526 tebuconazole ziram M-527 tebuconazole guazatin M-528 tebuconazole thiophanate- methyl M-529 tebuconazole chlorothalonil M-530 tebuconazole metrafenone M-531 triadimenol — M-532 triadimenol triticonazole M-533 triadimenol imazalil M-534 triadimenol prochloraz M-535 triadimenol carbendazim M-536 triadimenol thiabendazole M-537 triadimenol ethaboxam M-538 triadimenol hymexazole M-539 triadimenol pyrimethanil M-540 triadimenol fludioxonil M-541 triadimenol aldimorph M-542 triadimenol dodemorph M-543 triadimenol fenpropimorph M-544 triadimenol iprodione M-545 triadimenol captan M-546 triadimenol fenoxanil M-547 triadimenol probenazol M-548 triadimenol mancozeb M-549 triadimenol metiram M-550 triadimenol thiram M-551 triadimenol ziram M-552 triadimenol guazatin M-553 triadimenol thiophanate- methyl M-554 triadimenol chlorothalonil M-555 triadimenol metrafenone M-556 triticonazole — M-557 triticonazole imazalil M-558 triticonazole prochloraz M-559 triticonazole carbendazim M-560 triticonazole thiabendazole M-561 triticonazole ethaboxam M-562 triticonazole hymexazole M-563 triticonazole pyrimethanil M-564 triticonazole fludioxonil M-565 triticonazole aldimorph M-566 triticonazole dodemorph M-567 triticonazole fenpropimorph M-568 triticonazole iprodione M-569 triticonazole captan M-570 triticonazole fenoxanil M-571 triticonazole probenazol M-572 triticonazole mancozeb M-573 triticonazole metiram M-574 triticonazole thiram M-575 triticonazole ziram M-576 triticonazole guazatin M-577 triticonazole thiophanate- methyl M-578 triticonazole chlorothalonil M-579 triticonazole metrafenone M-580 imazalil — M-581 imazalil prochloraz M-582 imazalil carbendazim M-583 imazalil thiabendazole M-584 imazalil ethaboxam M-585 imazalil hymexazole M-586 imazalil pyrimethanil M-587 imazalil fludioxonil M-588 imazalil aldimorph M-589 imazalil dodemorph M-590 imazalil fenpropimorph M-591 imazalil iprodione M-592 imazalil captan M-593 imazalil fenoxanil M-594 imazalil probenazol M-595 imazalil mancozeb M-596 imazalil metiram M-597 imazalil thiram M-598 imazalil ziram M-599 imazalil guazatin M-600 imazalil thiophanate- methyl M-601 imazalil chlorothalonil M-602 imazalil metrafenone M-603 prochloraz — M-604 prochloraz carbendazim M-605 prochloraz thiabendazole M-606 prochloraz ethaboxam M-607 prochloraz hymexazole M-608 prochloraz pyrimethanil M-609 prochloraz fludioxonil M-610 prochloraz aldimorph M-611 prochloraz dodemorph M-612 prochloraz fenpropimorph M-613 prochloraz iprodione M-614 prochloraz captan M-615 prochloraz fenoxanil M-616 prochloraz probenazol M-617 prochloraz mancozeb M-618 prochloraz metiram M-619 prochloraz thiram M-620 prochloraz ziram M-621 prochloraz guazatin M-622 prochloraz thiophanate- methyl M-623 prochloraz chlorothalonil M-624 prochloraz metrafenone M-625 carbendazim — M-626 carbendazim thiabendazole M-627 carbendazim ethaboxam M-628 carbendazim hymexazole M-629 carbendazim pyrimethanil M-630 carbendazim fludioxonil M-631 carbendazim aldimorph M-632 carbendazim dodemorph M-633 carbendazim fenpropimorph M-634 carbendazim iprodione M-635 carbendazim captan M-636 carbendazim fenoxanil M-637 carbendazim probenazol M-638 carbendazim mancozeb M-639 carbendazim metiram M-640 carbendazim thiram M-641 carbendazim ziram M-642 carbendazim guazatin M-643 carbendazim thiophanate- methyl M-644 carbendazim chlorothalonil M-645 carbendazim metrafenone M-646 thiabendazole — M-647 thiabendazole ethaboxam M-648 thiabendazole hymexazole M-649 thiabendazole pyrimethanil M-650 thiabendazole fludioxonil M-651 thiabendazole aldimorph M-652 thiabendazole dodemorph M-653 thiabendazole fenpropimorph M-654 thiabendazole iprodione M-655 thiabendazole captan M-656 thiabendazole fenoxanil M-657 thiabendazole probenazol M-658 thiabendazole mancozeb M-659 thiabendazole metiram M-660 thiabendazole thiram M-661 thiabendazole ziram M-662 thiabendazole guazatin M-663 thiabendazole thiophanate- methyl M-664 thiabendazole chlorothalonil M-665 thiabendazole metrafenone M-666 ethaboxam — M-667 ethaboxam hymexazole M-668 ethaboxam pyrimethanil M-669 ethaboxam fludioxonil M-670 ethaboxam aldimorph M-671 ethaboxam dodemorph M-672 ethaboxam fenpropimorph M-673 ethaboxam iprodione M-674 ethaboxam captan M-675 ethaboxam fenoxanil M-676 ethaboxam probenazol M-677 ethaboxam mancozeb M-678 ethaboxam metiram M-679 ethaboxam thiram M-680 ethaboxam ziram M-681 ethaboxam guazatin M-682 ethaboxam thiophanate- methyl M-683 ethaboxam chlorothalonil M-684 ethaboxam metrafenone M-685 hymexazole — M-686 hymexazole pyrimethanil M-687 hymexazole fludioxonil M-688 hymexazole aldimorph M-689 hymexazole dodemorph M-690 hymexazole fenpropimorph M-691 hymexazole iprodione M-692 hymexazole captan M-693 hymexazole fenoxanil M-694 hymexazole probenazol M-695 hymexazole mancozeb M-696 hymexazole metiram M-697 hymexazole thiram M-698 hymexazole ziram M-699 hymexazole guazatin M-700 hymexazole thiophanate- methyl M-701 hymexazole chlorothalonil M-702 hymexazole metrafenone M-703 pyrimethanil — M-704 pyrimethanil fludioxonil M-705 pyrimethanil aldimorph M-706 pyrimethanil dodemorph M-707 pyrimethanil fenpropimorph M-708 pyrimethanil iprodione M-709 pyrimethanil captan M-710 pyrimethanil fenoxanil M-711 pyrimethanil probenazol M-712 pyrimethanil mancozeb M-713 pyrimethanil metiram M-714 pyrimethanil thiram M-715 pyrimethanil ziram M-716 pyrimethanil guazatin M-717 pyrimethanil thiophanate- methyl M-718 pyrimethanil chlorothalonil M-719 pyrimethanil metrafenone M-720 fludioxonil — M-721 fludioxonil aldimorph M-722 fludioxonil dodemorph M-723 fludioxonil fenpropimorph M-724 fludioxonil iprodione M-725 fludioxonil captan M-726 fludioxonil fenoxanil M-727 fludioxonil probenazol M-728 fludioxonil mancozeb M-729 fludioxonil metiram M-730 fludioxonil thiram M-731 fludioxonil ziram M-732 fludioxonil guazatin M-733 fludioxonil thiophanate- methyl M-734 fludioxonil chlorothalonil M-735 fludioxonil metrafenone M-736 aldimorph — M-737 aldimorph dodemorph M-738 aldimorph fenpropimorph M-739 aldimorph iprodione M-740 aldimorph captan M-741 aldimorph fenoxanil M-742 aldimorph probenazol M-743 aldimorph mancozeb M-744 aldimorph metiram M-745 aldimorph thiram M-746 aldimorph ziram M-747 aldimorph guazatin M-748 aldimorph thiophanate- methyl M-749 aldimorph chlorothalonil M-750 aldimorph metrafenone M-751 dodemorph — M-752 dodemorph fenpropimorph M-753 dodemorph iprodione M-754 dodemorph captan M-755 dodemorph fenoxanil M-756 dodemorph probenazol M-757 dodemorph mancozeb M-758 dodemorph metiram M-759 dodemorph thiram M-760 dodemorph ziram M-761 dodemorph guazatin M-762 dodemorph thiophanate- methyl M-763 dodemorph chlorothalonil M-764 dodemorph metrafenone M-765 fenpropimorph — M-766 fenpropimorph iprodione M-767 fenpropimorph captan M-768 fenpropimorph fenoxanil M-769 fenpropimorph probenazol M-770 fenpropimorph mancozeb M-771 fenpropimorph metiram M-772 fenpropimorph thiram M-773 fenpropimorph ziram M-774 fenpropimorph guazatin M-775 fenpropimorph thiophanate- methyl M-776 fenpropimorph chlorothalonil M-777 fenpropimorph metrafenone M-778 iprodione — M-779 iprodione captan M-780 iprodione fenoxanil M-781 iprodione probenazol M-782 iprodione mancozeb M-783 iprodione metiram M-784 iprodione thiram M-785 iprodione ziram M-786 iprodione guazatin M-787 iprodione thiophanate- methyl M-788 iprodione chlorothalonil M-789 iprodione metrafenone M-790 captan — M-791 captan fenoxanil M-792 captan probenazol M-793 captan mancozeb M-794 captan metiram M-795 captan thiram M-796 captan ziram M-797 captan guazatin M-798 captan thiophanate- methyl M-799 captan chlorothalonil M-800 captan metrafenone M-801 fenoxanil — M-802 fenoxanil probenazol M-803 fenoxanil mancozeb M-804 fenoxanil metiram M-805 fenoxanil thiram M-806 fenoxanil ziram M-807 fenoxanil guazatin M-808 fenoxanil thiophanate- methyl M-809 fenoxanil chlorothalonil M-810 fenoxanil metrafenone M-811 probenazol — M-812 probenazol mancozeb M-813 probenazol metiram M-814 probenazol thiram M-815 probenazol ziram M-816 probenazol guazatin M-817 probenazol thiophanate- methyl M-818 probenazol chlorothalonil M-819 probenazol metrafenone M-820 mancozeb — M-821 mancozeb metiram M-822 mancozeb thiram M-823 mancozeb ziram M-824 mancozeb guazatin M-825 mancozeb thiophanate- methyl M-826 mancozeb chlorothalonil M-827 mancozeb metrafenone M-828 metiram — M-829 metiram thiram M-830 metiram ziram M-831 metiram guazatin M-832 metiram thiophanate- methyl M-833 metiram chlorothalonil M-834 metiram metrafenone M-835 thiram — M-836 thiram ziram M-837 thiram guazatin M-838 thiram thiophanate- methyl M-839 thiram chlorothalonil M-840 thiram metrafenone M-841 ziram — M-842 ziram guazatin M-843 ziram thiophanate- methyl M-844 ziram chlorothalonil M-845 ziram metrafenone M-846 guazatin — M-847 guazatin thiophanate- methyl M-848 guazatin chlorothalonil M-849 guazatin metrafenone M-850 thiophanate- — methyl M-851 thiophanate- chlorothalonil methyl M-852 thiophanate- metrafenone methyl M-853 chlorothalonil — M-854 chlorothalonil metrafenone M-855 metrafenone —

The crystalline modification I and the one or more compound(s) of groups A.1-A.15 are usually applied in a weight ratio of from 500:1 to 1:100, preferably from 20:1 to 1:50, in particular from 5:1 to 1:20.

The same preferred mixture ratios apply also to combinations of modification I with fungicidal compounds IIA. Compounds IIB are usually combined with modification I in ratios from 100:1 to 1:100.

Depending on the desired effect, the application rates of the mixtures according to the invention are from 5 g/ha to 2000 g/ha, preferably from 50 to 1500 g/ha, in particular from 50 to 750 g/ha.

The crystalline modification I, the mixtures and the compositions according to the invention can be applied to any and all developmental stages, such as egg, larva, pupa, and adult. The pests may be controlled by contacting the target pest, its food supply, habitat, breeding ground or its locus with a pesticidally effective amount of the crystalline modification I, the mixtures or the compositions according to the invention.

“Locus” means a plant, seed, soil, area, material or environment in which a pest is growing or may grow.

In general, “pesticidally effective amount” means the amount of the crystalline modification I, the mixtures and the compositions according to the invention needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The pesticidally effective amount can vary for the various mixtures/compositions used in the invention. A pesticidally effective amount of the mixtures/compositions will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.

The crystalline modification I, the mixtures and the compositions according to the invention can also be employed for protecting plants from attack or infestation by insects, acarids or nematodes comprising contacting a plant, or soil or water in which the plant is growing.

In the context of the present invention, the term plant refers to an entire plant, a part of the plant or the propagation material of the plant, that is, the seed or the seedling.

Plants which can be treated with the crystalline modification I, the mixtures and the compositions according to the invention include all genetically modified plants or transgenic plants, e.g. crops which tolerate the action of herbicides or fungicides or insecticides owing to breeding, including genetic engineering methods, or plants which have modified characteristics in comparison with existing plants, which can be generated for example by traditional breeding methods and/or the generation of mutants, or by recombinant procedures.

Some of the inventive mixtures and compositions have systemic action and can therefore be used for the protection of the plant shoot against foliar pests as well as for the treatment of the seed and roots against soil pests. The term seed treatment comprises all suitable seed treatment techniques known in the art, such as, but not limited to, seed dressing, seed coating, seed dusting, seed soaking, seed film coating, seed multilayer coating, seed encrusting, seed dripping, and seed pelleting.

The present invention also comprises seeds coated with or containing the crystalline modification I or the mixtures or the compositions according to the invention.

The term seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corms, bulbs, fruit, tubers, grains, cuttings, cut shoots and the like and means in a preferred embodiment true seeds.

Suitable seed is seed of cereals, root crops, oil crops, vegetables, spices, ornamentals, for example seed of durum and other wheat, barley, oats, rye, maize (fodder maize and sugar maize/sweet and field corn), soybeans, oil crops, crucifers, cotton, sunflowers, bananas, rice, oilseed rape, turnip rape, sugarbeet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, pepper, cucumbers, melons, Brassica species, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias, geranium/pelargoniums, pansies and impatiens.

In addition, the crystalline modification I, the mixtures and the compositions according to the invention may also be used for the treatment seeds from plants, which tolerate the action of herbicides or fungicides or insecticides or nematicides owing to breeding, mutation and/or genetic engineering methods.

For example, the crystalline modification I, the mixtures and the compositions according to the invention can be employed in transgenic crops which are resistant to herbicides from the group consisting of the sulfonylureas (EP-A-0257993, U.S. Pat. No. 5,013,659), imidazolinones (see for example U.S. Pat. No. 6,222,100, WO 01/82685, WO 00/26390, WO 97/41218, WO 98/02526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073), glufosinate-type (see for example EP-A 242 236, EP-A 242 246) or glyphosate-type (see for example WO 92/00377) or in plants resistant towards herbicides selected from the group of cyclohexadienone/aryloxyphenoxypropionic acid herbicides (U.S. Pat. No. 5,162,602, U.S. Pat. No. 5,290,696, U.S. Pat. No. 5,498,544, U.S. Pat. No. 5,428,001, U.S. Pat. No. 6,069,298, U.S. Pat. No. 6,268,550, U.S. Pat. No. 6,146,867, U.S. Pat. No. 6,222,099, U.S. Pat. No. 6,414,222) or in transgenic crop plants, for example cotton, with the capability of producing Bacillus thuringiensis toxins (Bt toxins) which make the plants resistant to certain pests (EP-A 142 924, EP-A 193 259).

Furthermore, the crystalline modification I, the mixtures and the compositions according to the invention can be used also for the treatment of seeds from plants, which have modified characteristics in comparison with existing plants consist, which can be generated, for example by traditional breeding methods and/or the generation of mutants, or by recombinant procedures). For example, a number of cases have been described of recombinant modifications of crop plants for the purpose of modifying the starch synthesized in the plants (e.g. WO 92/11376, WO 92/14827, WO 91/19806) or of transgenic crop plants having a modified fatty acid composition (WO 91/13972).

The seed treatment application of the crystalline modification I, the mixtures and the compositions according to the invention is carried out by spraying or dusting the seeds before sowing of the plants and before emergence of the plants.

In the treatment of seeds the corresponding formulations are applied by treating the seeds with an effective amount of the crystalline modification I, the mixtures or the compositions according to the invention. Herein, the application rates of the crystalline modification I are generally from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in particular from 1 g to 2.5 kg per 100 kg of seed. For specific crops such as lettuce and onions the rates can be higher.

The mixtures and the compositions according to the invention are effective through both contact (via soil, glass, wall, bed net, carpet, plant parts or animal parts), and ingestion (bait, or plant part) and through trophallaxis and transfer.

Preferred application methods are into water bodies, via soil, cracks and crevices, pastures, manure piles, sewers, into water, on floor, wall, or by perimeter spray application and bait.

According to another preferred embodiment of the invention, for use against non-crop pests such as ants, termites, wasps, flies, mosquitoes, crickets, locusts, or cockroaches the mixtures and the compositions according to the invention are prepared into a bait preparation.

The bait can be a liquid, a solid or a semisolid preparation (e.g. a gel). The bait employed in the mixtures/compositions is a product which is sufficiently attractive to incite insects such as ants, termites, wasps, flies, mosquitoes, crickets etc. or cockroaches to eat it. This attractant may be chosen from feeding stimulants or para and/or sex pheromones readily known in the art.

Methods to control infectious diseases transmitted by insects (e.g. malaria, dengue and yellow fever, lymphatic filariasis, and leishmaniasis) with the inventive mixtures and their respective compositions also comprise treating surfaces of huts and houses, air spraying and impregnation of curtains, tents, clothing items, bed nets, tsetse-fly trap or the like. Insecticidal compositions for application to fibers, fabric, knitgoods, nonwovens, netting material or foils and tarpaulins preferably comprise a composition including the inventive mixtures, optionally a repellent and at least one binder.

The crystalline modification I, the mixtures and the compositions according to the invention can be used for protecting wooden materials such as trees, board fences, sleepers, etc. and buildings such as houses, outhouses, factories, but also construction materials, furniture, leathers, fibers, vinyl articles, electric wires and cables etc. from ants and/or termites, and for controlling ants and termites from doing harm to crops or human being (e.g. when the pests invade into houses and public facilities).

In the case of soil treatment or of application to the pests dwelling place or nest, the quantity of active ingredient ranges from 0.0001 to 500 g per 100 m², preferably from 0.001 to 20 g per 100 m².

Customary application rates in the protection of materials are, for example, from 0.01 g to 1000 g of active compound per m² treated material, desirably from 0.1 g to 50 g per m².

Insecticidal compositions for use in the impregnation of materials typically contain from 0.001 to 95 weight %, preferably from 0.1 to 45 weight %, and more preferably from 1 to 25 weight % of at least one repellent and/or insecticide.

For use in bait compositions, the typical content of active ingredient(s) is from 0.0001 weight % to 15 weight %, desirably from 0.001 weight % to 5% weight % of active compound. The composition used may also comprise other additives such as a solvent of the active material, a flavoring agent, a preserving agent, a dye or a bitter agent. Its attractiveness may also be enhanced by a special color, shape or texture.

For use in spray compositions, the content of the active ingredient(s) is from 0.001 to 80 weights %, preferably from 0.01 to 50 weight % and most preferably from 0.01 to 15 weight %.

For use in treating crop plants, the rate of application of the active ingredient(s) may be in the range of 0.1 g to 4000 g per hectare, desirably from 25 g to 600 g per hectare, more desirably from 50 g to 500 g per hectare.

It was also an object of the present invention to provide mixtures suitable for treating, controlling, preventing and protecting warm-blooded animals, including humans, and fish against infestation and infection by pests. Problems that may be encountered with pest control on or in animals and/or humans are similar to those described at the outset, namely the need for reduced dosage rates, and/or enhanced spectrum of activity and/or combination of knock-down activity with prolonged control and/or resistance management.

This invention also provides a method for treating, controlling, preventing and protecting warm-blooded animals, including humans, and fish against infestation and infection by pests of the orders Siphonaptera, Hymenoptera, Hemiptera, Orthoptera, Acarina, Phthiraptera, and Diptera, which comprises orally, topically or parenterally administering or applying to said animals a pesticidally effective amount of the crystalline modification I, the mixtures and the compositions according to the invention.

The invention also provides a process for the preparation of a composition for treating, controlling, preventing or protecting a warm-blooded animal or a fish against infestation or infection by pests of the Siphonaptera, Hymenoptera, Hemiptera, Orthoptera, Acarina, Phthiraptera, and Diptera orders which comprises a pesticidally effective amount of the crystalline modification I, the mixtures and the compositions according to the invention.

The above method is particularly useful for controlling and preventing infestations and infections in warm-blooded animals such as cattle, sheep, swine, camels, deer, horses, poultry, goats, dogs and cats as well as humans.

Infestations in warm-blooded animals and fish including, but not limited to, lice, biting lice, ticks, nasal bots, keds, biting flies, muscoid flies, flies, myiasitic fly larvae, chiggers, gnats, mosquitoes and fleas may be controlled, prevented or eliminated by the crystalline modification I, the mixtures and the compositions according to the invention.

For oral administration to warm-blooded animals, the crystalline modification I, the mixtures and the compositions according to the invention may be formulated as animal feeds, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drenches, gels, tablets, boluses and capsules. In addition, the crystalline modification I, the mixtures and the compositions according to the invention may be administered to the animals in their drinking water. For oral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the crystalline modification I, the mixtures and the compositions according to the invention.

Alternatively, the crystalline modification I, the mixtures and the compositions according to the invention may be administered to animals parenterally, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection. The crystalline modification I, the mixtures and the compositions according to the invention may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection. Alternatively, the crystalline modification I, the mixtures and the compositions according to the invention may be formulated into an implant for subcutaneous administration. In addition, the crystalline modification I, the mixtures and the compositions according to the invention may be transdermally administered to animals. For parenteral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the crystalline modification I, the mixtures and the compositions according to the invention.

The crystalline modification I, the mixtures and the compositions according to the invention may also be applied topically to the animals in the form of dips, dusts, powders, collars, medallions, sprays, spot-on and pour-on formulations. For topical application, dips and sprays usually contain 0.5 ppm to 5000 ppm and preferably 1 ppm to 3000 ppm of the crystalline modification I. In addition, the crystalline modification I may be formulated as ear tags for animals, particularly quadrupeds such as cattle and sheep.

The figure and examples below serve to illustrate the invention and are not to be understood as limiting it.

FIG. 1: X-ray powder diffractogram of modification I

FIG. 2: Differential scanning calorimetry thermogram of modification I

FIG. 3: X-ray powder diffractograms of two mixtures of modifications I and V

PREPARATION EXAMPLES

All preparation procedures below were conducted with two samples of solid fipronil as starting materials which were obtained according to procedures as described in WO 01/30760, with final crystallization of the product from a solvent mixture of monochlorobenzene/ethanole (% by weight of ethanol at crystallization start: 13%) at temperatures of 70° C. to 35° C. This solid form in X-ray powder diffractogram studies proved to be crystalline fipronil of a mixture of several crystalline modifications. This mixture has been characterized to consist of crystalline modification I and crystalline modifications V, as for the first time identified and described in a co-pending application. A least squares refinement with the Topas program with simulated X-ray powder diffractogram patterns from single crystal data of form I and form V shows that in these two example samples, the percentage of form I varies from 30% to 70%. X-ray powder diffractograms of the two samples are shown in FIG. 3.

Irrespective of the sample of solid fipronil used as starting material, the crystallization procedures given in the examples given below gave the same inventive modification I.

Example 1 Preparation of Modification I by Crystallization from Methanol

1 g of crystalline fipronil having a chemical purity of about 96% by weight was dissolved in 25 ml of methanol at 48 to 52° C. in a round bottomed flask. The solution was kept at this temperature while the solvent was slowly evaporated with a gentle flow of inert N₂ gas. The solvent was left to evaporate over night, after which the dry product of crystalline fipronil was cooled to 20 to 25° C. and analyzed. Crystallization yield >95%, melting point: 195° C. The material obtained has the X-ray powder diffractogram shown in FIG. 1 with the reflexes listed in Table 2 below.

Example 2 Preparation of Modification I by Crystallization from Isopropanol

1 g of crystalline fipronil having a chemical purity of about 96% by weight was dissolved in 25 g of isopropanol at 65 to 70° C. under reflux. The mixture was stirred at 65 to 70° C. until all the material was fully dissolved, after which the stirring was stopped. The heating was removed and the solution was cooled down to 20 to 25° C. with a rate of 1-5 K/min, and the flask was left open allowing the solvent to evaporate slowly at 20 to 25° C. for one week, after which the solvent had fully evaporated. Crystallization yield >95%, melting point: 194° C. The material obtained has the X-ray powder diffractogram shown in FIG. 1 with the reflexes listed in Table 2 below.

Example 3 Preparation of Modification I by Crystallization from Ethanol

1 g of crystalline fipronil having a chemical purity of about 96% by weight was dissolved in 25 g of ethanol at 65 to 70° C. under reflux. The mixture was stirred at 65 to 70° C. until all the material was fully dissolved, after which the stirring was stopped. The heating was removed and the solution was cooled down to 20 to 25° C. with a rate of 1-5 K/min, and the flask was left open allowing the solvent to evaporate slowly at 20 to 25° C. Crystallization yield >95%, melting point: 196° C. The material obtained has the X-ray powder diffractogram shown in FIG. 1 with the reflexes listed in Table 2 below.

Example 4 Preparation of Modification I by Crystallization from Ethyl Benzene

0.61 g of fipronil having chemical purity of >98% by weight was suspended in 15 ml of ethyl benzene. Stirring was applied and the suspension was heated up to 140° C. giving a clear solution. The heating was removed and the solution was cooled down to 25° C. with a cooling rate of −1K/min. Stirring (700 rpm) was applied also through out the cooling phase. The crystallization was detected to begin at 76-70° C. The solid product was filtrated and dried on filtration paper over night and then analyzed by PXRD to give the X-ray powder diffractogram shown in FIG. 1.

Example 5 Preparation of Modification I by Crystallization from Diisopropyl Benzene (mixture of m- and p-di isopropyl benzene, ratio 2:1)

1.0 g of fipronil having chemical purity of >98% by weight was suspended in 10 ml of di isopropyl benzene. Stirring was applied and the suspension was heated up to 150° C. giving a clear solution. The heating was removed and the solution was cooled down to 25° C. with a cooling rate of −1 K/min. Stirring (700 rpm) was applied also through out the cooling phase. The crystallization was detected to begin at 138-130° C. The solid product was filtrated and dried on filtration paper over night and then analyzed by PXRD to give the X-ray powder diffractogram shown in FIG. 1.

Example 6 Preparation of Modification I by Crystallization from n-Butyl Benzene

1.0 g of fipronil having chemical purity of >98% by weight was suspended in 10 ml of n-butyl benzene. Stirring was applied and the suspension was heated up to 150° C. giving a clear solution. The heating was removed and the solution was cooled down to 25° C. with a cooling rate of −1 K/min. Stirring (700 rpm) was applied also through out the cooling phase. The crystallization was detected to begin at 138-130° C. The solid product was filtrated and dried on filtration paper over night and then analyzed by PXRD to give the X-ray powder diffractogram shown in FIG. 1.

Example 7 Preparation of Modification I by Crystallization from CF₃-Benzene

1.0 g of fipronil having chemical purity of >98% by weight was suspended in 8 ml of CF₃-benzene. Stirring was applied and the suspension was heated up to 130° C. giving a clear solution. The heating was removed and the solution was cooled down to 25° C. with a cooling rate of −1 K/min. Stirring (700 rpm) was applied also through out the cooling phase. The crystallization was detected to begin at 105-95° C. The solid product was filtrated and dried on filtration paper over night and then analyzed by PXRD to give the X-ray powder diffractogram shown in FIG. 1.

Example 8 Preparation of Modification I by Crystallization from Acetonitrile

1 g of crystalline fipronil having a chemical purity of about 96% by weight was dissolved in 15 ml of isopropanol at 20 to 25° C. to give a clear solution. The solution was left to evaporate for 10 days in an open flask. The resulted crystalline solid was left to dry on a filter paper over night. The material obtained has the X-ray powder diffractogram shown in FIG. 1 with the reflexes listed in Table 2 below.

Example 9 Preparation of Modification I by Crystallization from DMSO by Addition of Water

0.6 g of fipronil having chemical purity of >98% by weight was dissolved in 2 ml of DMSO at 20 to 25° C. in a 10 ml test tube. The solution was stirred and 4 ml of water was added at once. The product crystallized immediately after the water addition. The solution was stirred at 20 to 25° C. for one hour. The solid was filtrated and left to dry on a filter paper over night. The solid was analyzed by PXRD to give the X-ray powder diffractogram shown in FIG. 1.

TABLE 2 2θ- and d-values of modification I 2θ (°) d (Å) 11.9 ± 0.2 7.45 ± 0.05 14.6 ± 0.2 6.07 ± 0.03 15.9 ± 0.2 5.57 ± 0.03 18.3 ± 0.2 4.84 ± 0.02 23.6 ± 0.2 3.76 ± 0.02 24.2 ± 0.2 3.67 ± 0.02 27.6 ± 0.2 3.23 ± 0.02 29.6 ± 0.2 3.01 ± 0.02 32.3 ± 0.2 2.77 ± 0.02

Analysis:

The X-ray powder diffractogram displayed in FIG. 1 was recorded using a Siemens D-5000 diffractometer (manufacturer: Bruker AXS) in reflection geometry in the range from 2θ=2°-60° with increments of 0.02° using Cu—Kα radiation at 25° C. The 2θ values found were used to calculate the stated interplanar spacing d. In FIG. 1, the intensity of the peaks (y-axis: linear intensity in counts) is plotted versus the 28 angle (x-axis in degrees 2θ).

The single crystal X-ray diffraction data was collected on a Bruker AXS CCD Detector using graphite Cu_(Kalfa) radiation. The structure was solved by using direct methods, refined, and expanded by using Fourier techniques with the SHELX software package (G. M. Sheldrick, SHELX-97, Universität Göttingen, 1997). Absorption correction was performed with SADABS software.

Melting points indicated herein refer to values determined on a Mettler hot stage in combination with a light microscope and represent equilibrium melting points.

DSC was performed on a Mettler Toledo DSC 822e module. Crystals taken from the mother liquor were blotted dry on filter paper and place in crimped but vented aluminum sample pans for the DCS experiment. The sample size in each case was 4 to 6 mg. The temperature range was typically 30° C. to 250° C. at a heating rate of 5° C./min. The samples were purged with a stream of nitrogen flowing at 150 ml/min for the DSC experiment.

Investigations of the effect of the temperature of nucleation and beginning of the crystallization to the modification of the crystalline end product carried out with Polyblock by HEL Ltd. The multi reactor crystallization system allows the monitoring of the crystallization process and change in turbidity with special reflectance turbidity probes by HEL. The heating/cooling mantle and thermostat “Julabo FP 50” as well as the turbidity probes were controlled with a PC. 

1-36. (canceled)
 37. A solid fipronil comprising at least 85% by weight of the crystalline modification I fipronil being present in the monoclinic system having the centrosymmetric space group C2/c and showing, in an X-ray powder diffractogram at 30° C., at least 5 of the following reflexes: d=7.45±0.1 Å  (1) d=6.07±0.07 Å  (2) d=5.57±0.05 Å  (3) d=4.84±0.05 Å  (4) d=3.76±0.05 Å  (5) d=3.67±0.05 Å  (6) d=3.23±0.05 Å  (7) d=3.01±0.05 Å  (8) d=2.77±0.05 Å  (9).
 38. The solid fipronil of claim 37, wherein the crystalline modification I has a melting point in the range of from 196 to 198° C.
 39. The solid fipronil of claims 38, wherein the crystalline modification I has a fipronil content of at least 98% by weight.
 40. The solid fipronil of claim 37, further comprising a form of solid fipronil that is different from the crystalline modification I.
 41. A process for preparing the crystalline modification I of claim 37, comprising: i) preparing a solution of a solid form of fipronil being different from the crystalline modification I in a solvent S comprising at least one alcohol A1, acetonitrile, dimethylsulfoxide, or at least one benzene derivative B1; ii) effecting crystallization of fipronil; and iii) isolating the resulting precipitate, wherein the alcohol A1 is selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-butanol, and tert-butanol, and the benzene derivative B1 is benzene, which may be substituted by one or more groups selected from the group consisting of halogen, cyano, C₁-C₆-alkyl, C₁-C₆-alkoxy, halogenmethyl, and nitro, and wherein, when the solvent S is pure acetonitrile, the crystallization step ii) is conducted at temperatures below 40° C. and when the solvent S is pure dimethylsulfoxide, the crystallization step ii) is conducted at temperatures below 80° C.
 42. The process of claim 41, wherein, in step i), the solvent S is selected from the group consisting of isopropanol, n-butanol, isobutanol, 2-butanol, and tert-butanol.
 43. The process of claim 41, wherein, in step i), the solvent S is selected from the group consisting of ethyl benzene, n-propyl benzene, isopropyl benzene, diisopropyl benzene, n-butyl benzene, tert-butyl benzene, s-butyl benzene, iso-butyl benzene, CF₃-benzene, 2-chloro toluene, 3-chloro toluene, and mesitylene.
 44. The process of claim 41, wherein, in step i), the solvent S is selected from the group consisting of (a) a pure alcohol A1, (b) a mixture of different alcohols A1, and (c) a mixture of one or more alcohols A1 with water.
 45. The process of claim 41, wherein, in step i), the solvent S is selected from the group consisting of (d) pure acetonitrile, (e) a mixture of acetonitrile with water and/or one or more polar solvents P, (f) pure DMSO, (g) a mixture of DMSO with water and/or one or more polar solvents P, (h) pure benzene derivative B1, (i) a mixture of one or more benzene derivatives B1 with one or more alcohols A1, and (j) a mixture of one or more benzene derivatives B1 with one or more polar solvents P; wherein the polar solvent P is selected from the group consisting of methanol, ethanol, propan-1-ol, propan-2-ol, butan-1-ol, butan-2-ol, tert-butanol, 2-methyl-propan-1-ol, 2-methyl-propan-2-ol, pentan-3-ol, 2-methyl butan-1-ol, 3-methyl butan-1-ol, 1,2-ethanediol, 1,3-propandiol, 1,2-propandiol, cyclohexanol, acetonitrile, propionitrile, acetone, butanone, pentan-2-one, pentan-3-one, 4-methyl-2-pentanone, 3-methyl-butan-2-one, 3,3-dimethyl-2-butanone, cyclohexanone, methylacetate, ethylacetate, isopropylacetate, N-butylacetate, isobutylacetate, diethylcarbonate, 2-butoxyethylacetate, dioxane, tetrahydrofuran, diethylether, 2-methyl-tetrahydrofuran, methyl-tert-butylether, dimethylformamide, dimethylacetamide, dimethylsulfoxide, nitromethane, and nitroethane.
 46. The process of claim 41, wherein the alcohol A1 is methanol.
 47. The process of claim 41, wherein the alcohol A1 is ethanol.
 48. The process of claim 41, wherein the alcohol A1 is isopropanol.
 49. The process of claim 41, wherein the solvent S is a mixture of methanol and water, wherein the content of water does not exceed 25% by weight.
 50. The process of claim 41, wherein the benzene derivative B1 is ethyl benzene.
 51. The process of claim 41, wherein the benzene derivative B1 is propyl benzene.
 52. The process of claim 41, wherein the benzene derivative B1 is butyl benzene.
 53. The process of claim 41, wherein the benzene derivative B1 is CF₃-benzene.
 54. The process of claim 41, wherein, in step ii), the crystallization of fipronil is effected by concentration of the solution obtained in step i).
 55. The process of claim 41, wherein step ii) is carried out in the presence of seed crystals of the crystalline modification I of claim
 38. 56. The process of claim 43, wherein the crystallization according to step ii) is effected by cooling the solution obtained in step i) at a cooling rate of between 5 to 20 K per hour.
 57. A synergistic pesticidal or parasiticidal mixture comprising, as active components, the solid fipronil of claim 37 and one or more pesticidal or parasiticidal compounds.
 58. A pesticidal or parasiticidal composition, comprising the solid fipronil of claim 37 and pesticidally or parasiticidally acceptable carriers and/or auxiliaries.
 59. The composition of claim 58 in the form of an aqueous suspension concentrate.
 60. The composition of claim 58 in the form of water-dispersible granules.
 61. The composition of claim 58 in the form of a water-dispersible powder.
 62. A method for controlling pests which comprises contacting the pests or their food supply, habitat, breeding grounds or their locus with a pesticidally effective amount of the solid fipronil of claim
 37. 63. A method for protecting a plant from infestation and attack by pests, which comprises applying to the foliage or stem of said plant a pesticidally effective amount of the solid fipronil of claim
 37. 64. The method of claim 63, wherein the solid fipronil is applied in an amount of from 5 g/ha to 2000 g/ha.
 65. A method of the protection of seed comprising contacting the seeds with the mixture of claim 57 in pesticidally effective amounts.
 66. The method of claim 65, wherein the mixture is applied in an amount of from 0.1 g to 10 kg per 100 kg of seeds.
 67. A seed comprising the mixture of claim 57 in an amount of from 0.1 g to 10 kg per 100 kg of seeds.
 68. A method for treating, controlling, preventing or protecting animals against infestation or infection by parasites which comprises orally, topically or parenterally administering or applying to the animals a parasiticidally effective amount of the mixture of claim
 57. 